Formulation for an led encapsulation material

ABSTRACT

The present invention relates to a formulation suitable for the preparation of a highly refractive encapsulation material with good barrier properties towards water vapor for an LED, to an encapsulation material for an LED having a high refractive index and good barrier properties towards water vapor which is obtainable from said formulation and to a light emitting device (LED) comprising said encapsulation material. The formulation comprises a polymer comprising a first repeating unit U1 and a second repeating unit U2; and a surface-modified nanoparticle, wherein the surface-modified nanoparticle does not contain any zirconium dioxide.

TECHNICAL FIELD

The present invention relates to a formulation suitable for the preparation of a highly refractive encapsulation material for a light emitting device (LED), to an encapsulation material for an LED having a high refractive index which is obtainable from said formulation and to an LED comprising said highly refractive encapsulation material. Moreover, the present invention relates to a method for preparing a formulation suitable for the preparation of a highly refractive encapsulation material for an LED. The present invention further relates to a method for producing an LED by using said formulation. The formulation according to the invention is particularly suitable for the preparation of an encapsulation material for LEDs, in particular for phosphor-converted LEDs (pc-LEDs) having a converter layer with high refractive index. Moreover, the formulation allows a more efficient processability due to a faster curing rate. The encapsulation material according to the present invention provides a high refractive index which shows a low temperature dependence and thereby allows the preparation of high-performance LEDs having an increased light output and an improved colour point stability. Moreover, the encapsulation material shows improved barrier properties towards water vapor.

BACKGROUND AND DESCRIPTION OF THE PRIOR ART

There is a high demand in the LED industry to find suitable encapsulation materials for LEDs. Such materials face several challenges:

-   -   i. The encapsulation material has to withstand high temperatures         without degradation in mechanical and/or optical properties.     -   ii. The encapsulation material needs to have, in addition to         optical clarity and high temperature tolerance, the advantageous         property of a high refractive index.     -   iii. The capability of the encapsulation material to withstand         exposure to radiation of high intensity needs to be high.     -   iv. There is a need for encapsulation materials that can be         varied in elastic modulus across a wide range from very soft gel         materials to hard plastic materials.

LEDs can generate both high thermal flux and high optical flux. The LED package as well as the encapsulation material need to perform stably when exposed to heat and/or radiation (ultra-violet (UV) and/or visible (VIS) radiation). The right encapsulation material plays a major role in improving LED performance. So far, many encapsulation materials suffer from, among other, loss of transmittance during the lifetime of usage of the LED. In the following, advantages and remaining disadvantages of the main encapsulation materials are shown. Silicon-based materials are currently dominating the market because of their advantageous optical, mechanical and aging properties. Silicone reflectors improve brightness performance, show superior heat resistance and photo-thermal stability. With silicone-based reflectors there is minor degradation of the LED light intensity; they reflect light with a high efficiency of more than 98%. Silicones as protective films on chips show high heat resistance. The silicone can be compounded with a phosphor to make a white LED. Silicones can be dispensed or molded easily. Main applications are general lighting products such as LEDs and backlighting products in liquid crystal displays (LCDs).

One of the disadvantages of silicones is that they are highly transmissive and gas permeable. At elevated temperatures, chemical contaminants such as volatile organic compounds (VOCs) outgassing from the circuit board can cause discolouration. VOCs can accelerate the degradation of LEDs or impair the performance of LEDs. The effect of chemical incompatibility was seen in blue and white LEDs but not in red or green LEDs. Silicones are also permeable for moisture which enhances degradation and reduces the LED performance. Another disadvantage of silicones is the high CTE (320 ppm/° C., Electronic Packaging and Interconnection Handbook). The refractive index should also be higher.

The advantages of glass are superior optical properties and durability. That makes it attractive for high end applications. But clear disadvantages of glass are its incompatibility with standard LED manufacturing processes.

Epoxides are known for their excellent adhesion, chemical and heat resistance, good-to-excellent mechanical properties, and very good electrical insulating properties. But epoxides have poor aging characteristics. They show poor moisture resistance due to high water absorption and especially poor light resistance due to low transmittance for short wavelength light.

The choice of a suitable encapsulation material is highly driven by its aging stability against UV and high temperature as well as its processability. Encapsulation materials and the corresponding polymer formulations from which they are prepared for the manufacturing of LEDs need to satisfy several requirements. Besides optimal barrier properties towards water vapor and mechanical and optical stability, a high refractive index is required. The refractive index of a typical Gallium Nitride LED chip is about 2.4. The light leaving the LED chip into an encapsulation material having a lower refractive index is limited by total reflection on the interface. A higher refractive index of the encapsulation material mitigates this effect and therefore increases the brightness of the LED. So far, phenyl silicones with a refractive index of up to 1.54 are used as high refractive index encapsulation materials. The drawback of such materials is the presence of aromatic groups which limits their thermal and optical stability. Furthermore, the mixing of silicones with nanoparticles having a high refractive index to prepare stable dispersions is difficult, due to the incompatibility of silicones with most other materials leading to aggregation of the nanoparticles.

Hence, there is a strong need for new encapsulation materials which have a high refractive index with a low temperature dependence and which allow for the preparation of high-performance LEDs with an increased light output, improved colour point stability and barrier properties towards water vapor. Moreover, there is a strong need for new formulations allowing an efficient preparation of the above-mentioned new encapsulation materials.

Until now, no LED encapsulation materials have been reported which have a high refractive index and high transparency accompanied by resistance to yellowing caused by thermal degradation above 150° aging in air (Kim et al., 2010, Chemistry of Materials).

WO 2012/067766 discloses LEDs comprising a polysilazane bonding layer. The bonding layer typically further comprises a (meth)acrylate monomer.

WO 2014/062871 A1 relates to composite materials for LEDs including a matrix and at least one filler, wherein the matrix is a core-shell particle assembly containing an inorganic core and a polymeric shell. The inorganic core may be formed from aluminum nitride, aluminum oxide, cadmium telluride, barium titanate, titanium dioxide, zirconium dioxide, zinc sulfide, or combinations thereof. The polymeric shell may be formed from acrylic polymers, polystyrene, styrene copolymers, polysiloxanes, polyethylene, polypropylene or combination thereof.

WO 2015/007778 A1 introduces new encapsulation materials for LEDs which are based on specific organopolysilazanes. Polysilazane/polysiloxane copolymers have been described in US 2015/0188006 A1 as encapsulation polymers. Polysilazane/polysiloxane block copolymers are also known from WO 2002/068535 A1.

EP 2 733 117 A2 relates to inorganic fine particle scattering films and a manufacturing method thereof, wherein an inorganic fine particle layer comprising pores is formed on an LED interface or a transparent substrate so as to achieve a high light extraction effect through a light scattering effect, and a planarizing layer is formed on the inorganic fine particle layer so as to show a high flatness and a high hardness.

US 2009/0272996 A1 relates to phosphor-converted LEDs, wherein the light extraction efficiency and the colour temperature distribution uniformity are improved by the introduction of both nanoparticles and light scattering particles proximate to the light source.

However, the LED encapsulation materials known from the state of the art leave some room for improvement, particularly with regard to better LED properties such as an increased efficiency and improved colour point stability.

TECHNICAL PROBLEM AND OBJECT OF THE PRESENT INVENTION

Various polymer formulations for the preparation of encapsulation materials for LEDs have been proposed. However, there is a continuing need to improve these polymer formulations and the obtained encapsulation materials so that they allow an efficient production of LEDs having an increased efficiency due to an increased light output, an improved colour point stability, especially after aging, and a converter layer with enhanced barrier properties towards water vapor. Moreover, there is a strong need for new encapsulation materials having a high refractive index which depends minimally from temperature.

It is therefore an aim of the present invention to overcome the disadvantages in the prior art and to provide a new polymer formulation which is suitable for the preparation of a highly refractive encapsulation material for LEDs having an increased light output and an improved colour point stability. It is a further object of the present invention to provide a method for preparing a polymer formulation which is suitable for the preparation of a highly refractive encapsulation material for LEDs. Moreover, it is an object of the present invention to provide an LED comprising said highly refractive encapsulation material and having enhanced barrier properties towards water vapor. Beyond that, it is an object of the present invention to provide a method for preparing an LED by using said polymer formulation in an efficient way.

The polymer formulation according to the present invention is particularly suitable for the preparation of an encapsulation material for LEDs, in particular for phosphor-converted LEDs (pc-LEDs) having a converter layer with a high refractive index. Moreover, the polymer formulation exhibits a faster curing rate when compared to conventional polymer formulations and thereby allows a more efficient processability. The encapsulation material of the present invention provides a high refractive index with a low temperature dependence and thereby allows for the production of high-performance LEDs having an increased light output, improved colour point stability, and enhanced barrier properties towards water vapor.

SUMMARY OF THE INVENTION

The present inventors have surprisingly found that the above objects can be solved either individually or in any combination by a formulation comprising:

-   -   a polymer containing a first repeating unit U¹ and a second         repeating unit U², wherein the first repeating unit U¹ is         represented by formula (I) and the second repeating unit U² is         represented by formula (II):

—[—SiR¹R²—NR⁵—]—  (I)

—[—SiR³R⁴—[—O—SiR³R⁴—]_(a)—NR⁵—]—  (II)

wherein R¹, R², R³ , R⁴ and R⁵ are at each occurrence independently from each other selected from the group consisting of hydrogen, organyl and organoheteryl, and a is an integer from 1 to 60; and

-   -   surface-modified nanoparticles, wherein the surface-modified         nanoparticles do not contain any zirconium dioxide.

Moreover, an encapsulation material for an LED is provided, wherein the encapsulation material is obtainable by

-   -   (a) providing a formulation according to the invention; and     -   (b) curing said formulation at a temperature of 70 to 300° C.         for a period of 1 to 24 h.

There is further provided an LED comprising the inventive encapsulation material.

In addition, a method for preparing a formulation according to the invention is provided, wherein a polymer containing a first repeating unit U¹ and a second repeating unit U² is mixed with a dispersion of surface-modified nanoparticles, wherein the surface-modified nanoparticles do not contain any zirconium dioxide.

Finally, the present invention provides a method for producing an LED comprising the following steps:

-   -   (a) applying a formulation according to the invention to an LED         precursor; and     -   (b) curing the formulation at a temperature of 70 to 300° C. for         a period of 1 to 24 h.

Further embodiments which are preferred are described in the dependent claims below.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 shows the absorption spectrum of the surface-modified nanoparticles of Dispersion 1 dispersed at 40 weight % in PGMEA.

FIG. 2 shows the particle size distribution of the surface-modified nanoparticles of Dispersion 1 dispersed at 1 weight % in PGMEA as measured with a dynamic light scattering instrument.

FIG. 3 shows the refractive index as a function of temperature:

-   -   ▪ Dispersion 1:Polymer 1=80:20     -   ∘ Dispersion 1:Polymer 1=50:50     -   ♦ Polymer 2     -   □ Methyl Silicone     -   . . . . . Linear fit (▪, ∘, and ♦)     -   - - - - - Linear fit (□)

FIG. 4 shows the relative change of refractive index as a function of temperature in respect to 25° C.:

-   -   ▪ Dispersion 1:Polymer 1=80:20     -   ∘ Dispersion 1:Polymer 1=50:50     -   ♦ Polymer 2     -   □ Methyl Silicone     -   . . . . . Linear fit (▪, ∘, and ♦)     -   - - - - - Linear fit (□)

DETAILED DESCRIPTION OF THE INVENTION

The term “encapsulation material” or “encapsulant” as used herein means a material which covers or encloses a converter. Preferably, the encapsulation material forms part of a converter layer which contains one or more converters. The converter layer may be either arranged directly on a semiconductor light source (LED chip) or alternatively arranged remote therefrom, depending on the respective type of application. The converter layer may be present as a film having different thicknesses or having an uniform thickness. The encapsulation material forms a barrier against the external environment of the LED device, thereby protecting the converter and/or the LED chip. The encapsulating material is preferably in direct contact with the converter and/or the LED chip. Usually, the encapsulation material forms part of an LED package comprising an LED chip and/or lead frame and/or gold wire, and/or solder (flip chip), the filling material, converter and a primary and secondary optic. The encapsulation material may cover an LED chip and/or lead frame and/or gold wire and may contain a converter. The encapsulation material has the function of a surface protection material against external environmental influences and guarantees long term reliability that means aging stability. Preferably, the converter layer containing the encapsulation material has a thickness of 1 μm to 1 cm, more preferably of 10 μm to 1 mm.

The external environmental influence may be chemical or physical such as e.g. moisture, chemicals (e.g. acids, bases, oxygen within others), temperature, or mechanical impact or stress. The encapsulant shows temperature resistance between −55 to +260° C. The encapsulation material of the present invention can act as a binder for the converter, such as a phosphor powder or a quantum material (e.g. quantum dots). The encapsulant can also be shaped in order to provide primary optic functions (lens).

It is noted that the terms “layer” and “layers” are used interchangeably throughout the application. A person of ordinary skill in the art will understand that a single “layer” of material may actually comprise several individual layers of material. Likewise, several “layers” of material may be considered functionally as a single layer. In other words the term “layer” does not denote a homogenous layer of material. A single “layer” may contain various material concentrations and compositions that are localized in sub-layers. These sub-layers may be formed in a single formation step or in multiple steps. Unless specifically stated otherwise, it is not intended to limit the scope of the invention as embodied in the claims by describing an element as comprising a “layer” or “layers” of material.

The term “LED” as used herein means an LED device comprising one or more of a semiconductor light source (LED chip), lead frame, wiring, solder (flip chip), converter, filling material, encapsulation material, primary optics and/or secondary optics. An LED may be prepared from an LED precursor containing a semiconductor light source (LED chip) and/or lead frame and/or gold wire and/or solder (flip chip). In an LED precursor neither the LED chip nor the converter is enclosed by an encapsulation material. Usually, the encapsulation material and the converter form part of a converter layer. Such converter layer may be either arranged directly on an LED chip or alternatively arranged remote therefrom, depending on the respective type of application.

The term “converter” as used herein means a material that converts light of a first wavelength to light of a second wavelength, wherein the second wavelength is different from the first wavelength. Converters are phosphors or quantum materials.

A “phosphor” is a fluorescent inorganic material which contains one or more light emitting centers. The light emitting centers are formed by activator elements such as e.g. atoms or ions of rare earth metal elements, for example La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu, and/or atoms or ions of transition metal elements, for example Cr, Mn, Fe, Co, Ni, Cu, Ag, Au and Zn, and/or atoms or ions of main group metal elements, for example Na, TI, Sn, Pb, Sb and Bi. Examples of suitable phosphors include phosphors based on garnet, silicate, orthosilicate, thiogallate, sulfide, nitride, silicon-based oxynitride, nitridosilicate, nitridoaluminiumsilicate, oxonitridosilicate, oxonitridoaluminiumsilicate and rare earth doped sialon. Phosphors within the meaning of the present application are materials which absorb electromagnetic radiation of a specific wavelength range, preferably blue and/or ultraviolet (UV) electromagnetic radiation, and convert the absorbed electromagnetic radiation into electromagnetic radiation having a different wavelength range, preferably visible (VIS) light such as violet, blue, green, yellow, orange or red light.

A “quantum material” is a semiconductor nanoparticle forming a class of nanomaterials with physical properties that are widely tunable by controlling particle size, composition and shape. Among the most evident size dependent property of this class of materials is the tunable fluorescence emission. The tunability is afforded by the quantum confinement effect, where reducing particle size leads to a ‘particle in a box’ behavior, resulting in a blue shift of the band gap energy and hence the light emission. For example, in this manner, the emission of CdSe nanoparticles can be tuned from 660 nm for particles of diameter of ˜6.5 nm, to 500 nm for particles of diameter of ˜2 nm. Similar behavior can be achieved for other semiconductors when prepared as nanoparticles allowing for broad spectral coverage from the UV (using ZnSe, CdS for example) throughout the visible (using CdSe, InP for example) to the near-IR (using InAs for example). Changing the nanoparticle shape was demonstrated for several semiconductor systems, where especially prominent is the rod shape. Nanorods show properties that are modified from the spherical particles. For example, they exhibit emission that is polarized along the long rod axis, while spherical particles exhibit unpolarized emission. Moreover, we showed that nanorods have advantageous properties in optical gain, presenting potential for their use as laser materials (Banin et al., Adv. Mater., (2002) 14, 317). Single nanorods were also shown to exhibit a unique behavior under external electric fields—the emission can be switched on and off reversibly (Banin et. al., Nano Letters., (2005) 5, 1581).

“Nanoparticles” as used herein are particles with a diameter of <100 nm, preferably ≤95 nm, more preferably ≤90 nm, even more preferably ≤85 nm, even more preferably ≤80 nm, even more preferably ≤75 nm, even more preferably ≤70 nm, even more preferably ≤65 nm, even more preferably ≤60 nm, even more preferably ≤55 nm, even more preferably ≤50 nm, even more preferably ≤45 nm, even more preferably ≤40 nm, even more preferably ≤35 nm, even more preferably ≤30 nm, even more preferably ≤25 nm, and most preferably ≤20 nm.

The term “polymer” includes, but is not limited to, homopolymers, copolymers, for example, block, random, and alternating copolymers, terpolymers, quaterpolymers, etc., and blends and modifications thereof. Furthermore, unless otherwise specifically limited, the term “polymer” shall include all possible configurational isomers of the material. These configurations include, but are not limited to isotactic, syndiotactic, and atactic symmetries. A polymer is a molecule of high relative molecular mass, the structure of which essentially comprises the multiple repetition of units (i.e. repeating units) derived, actually or conceptually, from molecules of low relative mass (i.e. monomers).

The term “monomer” as used herein refers to a molecule which can undergo polymerization thereby contributing constitutional units (repeating units) to the essential structure of a polymer.

The term “homopolymer” as used herein stands for a polymer derived from one species of (real, implicit or hypothetical) monomer.

The term “copolymer” as used herein generally means any polymer derived from more than one species of monomer, wherein the polymer contains more than one species of corresponding repeating unit. In one embodiment the copolymer is the reaction product of two or more species of monomer and thus comprises two or more species of corresponding repeating unit. It is preferred that the copolymer comprises two, three, four, five or six species of repeating unit. Copolymers that are obtained by copolymerization of three monomer species can also be referred to as terpolymers. Copolymers that are obtained by copolymerization of four monomer species can also be referred to as quaterpolymers. Copolymers may be present as block, random, and/or alternating copolymers.

The term “block copolymer” as used herein stands for a copolymer, wherein adjacent blocks are constitutionally different, i.e. adjacent blocks comprise repeating units derived from different species of monomer or from the same species of monomer but with a different composition or sequence distribution of repeating units.

Further, the term “random copolymer” as used herein refers to a polymer formed of macromolecules in which the probability of finding a given repeating unit at any given site in the chain is independent of the nature of the adjacent repeating units. Usually, in a random copolymer, the sequence distribution of repeating units follows Bernoullian statistics.

The term “alternating copolymer” as used herein stands for a copolymer consisting of macromolecules comprising two species of repeating units in alternating sequence.

For the purposes of the present application the term “organyl” is used to denote any organic substituent group, regardless of functional type, having one free valence at a carbon atom.

For the purposes of the present application the term “organoheteryl” is used to denote any univalent group containing carbon, which is thus organic, but which has the free valence at an atom other than carbon being a heteroatom.

As used herein, the term “heteroatom” will be understood to mean an atom in an organic compound that is not a H- or C-atom, and preferably will be understood to mean N, O, S, P, Si, Se, As, Te or Ge.

An organyl or organoheteryl group comprising a chain of 3 or more C atoms may be straight-chain, branched and/or cyclic, including spiro and/or fused rings.

Preferred organyl and organoheteryl groups include alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy and alkoxycarbonyloxy, each of which is optionally substituted and has 1 to 40, preferably 1 to 25, very preferably 1 to 18 C atoms, furthermore optionally substituted aryl or aryloxy having 6 to 40, preferably 6 to 25 C atoms, furthermore alkylaryloxy, arylcarbonyl, aryloxycarbonyl, arylcarbonyloxy and aryloxycarbonyloxy, each of which is optionally substituted and has 6 to 40, preferably 7 to 40 C atoms, wherein all these groups do optionally contain one or more heteroatoms, preferably selected from N, O, S, P, Si, Se, As, Te and Ge.

The organyl or organoheteryl group may be a saturated or unsaturated acyclic group, or a saturated or unsaturated cyclic group. Unsaturated acyclic or cyclic groups are preferred, especially aryl, alkenyl and alkynyl groups (especially ethynyl). Where the C₁-C₄₀ organyl or organoheteryl group is acyclic, the group may be straight-chain or branched. The C₁-C₄₀ organyl or organoheteryl group includes for example: a C₁-C₄₀ alkyl group, a C₁-C₄₀ fluoroalkyl group, a C₁-C₄₀ alkoxy or oxaalkyl group, a C₂-C₄₀ alkenyl group, a C₂-C₄₀ alkynyl group, a C₃-C₄₀ allyl group, a C₄-C₄₀ alkyldienyl group, a C₄-C₄₀ polyenyl group, a C₂-C₄₀ ketone group, a C₂-C₄₀ ester group, a C₆-C₁₈ aryl group, a C₆-C₄₀ alkylaryl group, a C₆-C₄₀ arylalkyl group, a C₄-C₄₀ cycloalkyl group, a C₄-C₄₀ cycloalkenyl group, and the like. Preferred among the foregoing groups are a C₁-C₂₀ alkyl group, a C₁-C₂₀ fluoroalkyl group, a C₂-C₂₀ alkenyl group, a C₂-C₂₀ alkynyl group, a C₃-C₂₀ allyl group, a C₄-C₂₀ alkyldienyl group, a C₂-C₂₀ ketone group, a C₂-C₂₀ ester group, a C₆-C₁₂ aryl group, and a C₄-C₂₀ polyenyl group, respectively. Also included are combinations of groups having carbon atoms and groups having heteroatoms, such as e.g. an alkynyl group, preferably ethynyl, that is substituted with a silyl group, preferably a trialkylsilyl group.

The terms “aryl” and “heteroaryl” as used herein preferably mean a mono-, bi- or tricyclic aromatic or heteroaromatic group with 4 to 30 ring C atoms that may also comprise condensed rings and is optionally substituted with one or more groups L, wherein L is selected from halogen, —CN, —NC, —NCO, —NCS, —OCN, —SCN, —C(═O)NR⁰R⁰⁰, —C(═O)X⁰, —C(═O)R⁰, —NH₂, —NR⁰R⁰⁰, —SH, —SR⁰, SO₃H, SO₂R⁰, —OH, —NO₂, —CF₃, —SF₅, optionally substituted silyl, or organyl or organoheteryl with 1 to 40 C atoms that is optionally substituted and optionally comprises one or more heteroatoms, and is preferably alkyl, alkoxy, thiaalkyl, alkylcarbonyl, alkoxycarbonyl or alkoxycarbonyloxy with 1 to 20 C atoms that is optionally fluorinated, and R⁰, R⁰⁰, X⁰ have the meanings given above and below.

Very preferred substituents L are selected from halogen, most preferably F, or alkyl, alkoxy, oxaalkyl, thioalkyl, fluoroalkyl and fluoroalkoxy with 1 to 12 C atoms or alkenyl, and alkynyl with 2 to 12 C atoms.

Especially preferred aryl and heteroaryl groups are phenyl, phenyl wherein one or more CH groups are replaced by N, naphthalene, thiophene, selenophene, thienothiophene, dithienothiophene, fluorene and oxazole, all of which can be unsubstituted, mono- or polysubstituted with Las defined above. Very preferred rings are selected from pyrrole, preferably N-pyrrole, furan, pyridine, preferably 2- or 3-pyridine, pyrimidine, pyridazine, pyrazine, triazole, tetrazole, pyrazole, imidazole, isothiazole, thiazole, thiadiazole, isoxazole, oxazole, oxadiazole, thiophene, preferably 2-thiophene, selenophene, preferably 2-selenophene, thieno[3,2-b]thiophene, thieno[2,3-b]thiophene, furo[3,2-b]furan, furo[2,3-b]furan, seleno[3,2-b]selenophene, seleno[2,3-b]selenophene, thieno[3,2-b]selenophene, thieno[3,2-b]furan, indole, isoindole, benzo[b]furan, benzo[b]thiophene, benzo[1,2-b; 4,5-b′]dithiophene, benzo[2,1-b; 3,4-b′]dithiophene, quinole, 2-methylquinole, isoquinole, quinoxaline, quinazoline, benzotriazole, benzimidazole, benzothiazole, benzisothiazole, benzisoxazole, benzoxadiazole, benzoxazole, benzothiadiazole, all of which can be unsubstituted, mono- or polysubstituted with L as defined above. Further examples of aryl and heteroaryl groups are those selected from the groups shown hereinafter.

An alkyl or alkoxy radical, i.e. where the terminal CH₂ group is replaced by —O—, can be straight-chain or branched. It is preferably straight-chain (or linear). Suitable examples of such alkyl and alkoxy radical are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy, heptoxy, octoxy, nonoxy, decoxy, undecoxy, dodecoxy, tridecoxy or tetradecoxy. Preferred alkyl and alkoxy radicals have 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms. Suitable examples of such preferred alkyl and alkoxy radicals may be selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy, heptoxy, octoxy, nonoxy and decoxy.

An alkenyl group, wherein one or more CH₂ groups are replaced by —CH═CH— can be straight-chain or branched. It is preferably straight-chain, has 2 to 10 C atoms and accordingly is preferably vinyl, prop-1-enyl, or prop-2-enyl, but-1-enyl, but-2-enyl or but-3-enyl, pent-1-enyl, pent-2-enyl, pent-3-enyl or pent-4-enyl, hex-1-enyl, hex-2-enyl, hex-3-enyl, hex-4-enyl or hex-5-enyl, hept-1-enyl, hept-2-enyl, hept-3-enyl, hept-4-enyl, hept-5-enyl or hept-6-enyl, oct-1-enyl, oct-2-enyl, oct-3-enyl, oct-4-enyl, oct-5-enyl, oct-6-enyl or oct-7-enyl, non-1-enyl, non-2-enyl, non-3-enyl, non-4-enyl, non-5-enyl, non-6-enyl, non-7-enyl or non-8-enyl, dec-1-enyl, dec-2-enyl, dec-3-enyl, dec-4-enyl, dec-5-enyl, dec-6-enyl, dec-7-enyl, dec-8-enyl or dec-9-enyl.

Especially preferred alkenyl groups are C₂-C₇-1E-alkenyl, C₄-C₇-3E-alkenyl, C₅-C₇-4-alkenyl, C₆-C₇-5-alkenyl and C₇-6-alkenyl, in particular C₂-C₇-1E-alkenyl, C₄-07-3E-alkenyl and C₅-C₇-4-alkenyl. Examples for particularly preferred alkenyl groups are vinyl, 1E-propenyl, 1E-butenyl, 1E-pentenyl, 1E-hexenyl, 1E-heptenyl, 3-butenyl, 3E-pentenyl, 3E-hexenyl, 3E-heptenyl, 4-pentenyl, 4Z-hexenyl, 4E-hexenyl, 4Z-heptenyl, 5-hexenyl, 6-heptenyl and the like. Alkenyl groups having up to 5 C atoms are generally preferred.

An oxaalkyl group, i.e. where one CH₂ group is replaced by —O—, is preferably straight-chain 2-oxapropyl (=methoxymethyl), 2-(ethoxymethyl) or 3-oxabutyl (=2-methoxyethyl), 2-, 3-, or 4-oxapentyl, 2-, 3-, 4-, or 5-oxahexyl, 2-, 3-, 4-, 5-, or 6-oxaheptyl, 2-, 3-, 4-, 5-, 6- or 7-oxaoctyl, 2-, 3-, 4-, 5-, 6-, 7- or 8-oxanonyl or 2-, 3-, 4-, 5-, 6-,7-, 8- or 9-oxadecyl, for example. Oxaalkyl, i.e. where one CH₂ group is replaced by —O—, is preferably straight-chain 2-oxapropyl (=methoxymethyl), 2-(=ethoxymethyl) or 3-oxabutyl (=2-methoxyethyl), 2-, 3-, or 4-oxapentyl, 2-, 3-, 4-, or 5-oxahexyl, 2-, 3-, 4-, 5-, or 6-oxaheptyl, 2-, 3-, 4-, 5-, 6- or 7-oxaoctyl, 2-, 3-, 4-, 5-, 6-, 7- or 8-oxanonyl or 2-, 3-, 4-, 5-, 6-,7-, 8- or 9-oxadecyl, for example.

In an alkyl group wherein one CH₂ group is replaced by —O— and one by —C(O)—, these radicals are preferably neighboured. Accordingly these radicals together form a carbonyloxy group —C(O)—O— or an oxycarbonyl group —O—C(O)—. Preferably this group is straight-chain and has 2 to 6 C atoms. It is accordingly preferably selected from the group consisting of acetyloxy, propionyloxy, butyryloxy, pentanoyloxy, hexanoyloxy, acetyloxymethyl, propionyloxymethyl, butyryloxymethyl, pentanoyloxymethyl, 2-acetyloxyethyl, 2-propionyloxyethyl, 2-butyryloxyethyl, 3-acetyloxypropyl, 3-propionyloxypropyl, 4-acetyloxybutyl, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl, pentoxycarbonyl, methoxycarbonylmethyl, ethoxy-carbonylmethyl, propoxycarbonylmethyl, butoxycarbonylmethyl, 2-(methoxycarbonyl)ethyl, 2-(ethoxycarbonyl)ethyl, 2-(propoxy-carbonyl)ethyl, 3-(methoxycarbonyl)propyl, 3-(ethoxycarbonyl)propyl, and 4-(methoxycarbonyl)-butyl.

An alkyl group wherein two or more CH₂ groups are replaced by —O— and/or —C(O)O— can be straight-chain or branched. It is preferably straight-chain and has 3 to 12 C atoms. Accordingly it is preferably selected from the group consisting of bis-carboxy-methyl, 2,2-bis-carboxy-ethyl, 3,3-bis-carboxy-propyl, 4,4-bis-carboxy-butyl, 5,5-bis-carboxy-pentyl, 6,6-bis-carboxy-hexyl, 7,7-bis-carboxy-heptyl, 8,8-bis-carboxy-octyl, 9,9-bis-carboxy-nonyl, 10,10-bis-carboxy-decyl, bis-(methoxycarbonyl)-methyl, 2,2-bis-(methoxycarbonyl)-ethyl, 3,3-bis-(methoxycarbonyl)-propyl, 4,4-bis-(methoxycarbonyl)-butyl, 5,5-bis-(methoxycarbonyl)-pentyl, 6,6-bis-(methoxycarbonyl)-hexyl, 7,7-bis-(methoxycarbonyl)-heptyl, 8,8-bis-(methoxycarbonyl)-octyl, bis-(ethoxycarbonyl)-methyl, 2,2-bis-(ethoxycarbonyl)-ethyl, 3,3-bis-(ethoxycarbonyl)-propyl, 4,4-bis-(ethoxycarbonyl)-butyl, and 5,5-bis-(ethoxycarbonyl)-hexyl.

A thioalkyl group, i.e. where one CH₂ group is replaced by —S—, is preferably straight-chain thiomethyl (—SCH₃), 1-thioethyl (—SCH₂CH₃), 1-thiopropyl (=—SCH₂CH₂CH₃), 1-(thiobutyl), 1-(thiopentyl), 1-(thiohexyl), 1-(thioheptyl), 1-(thiooctyl), 1-(thiononyl), 1-(thiodecyl), 1-(thioundecyl) or 1-(thiododecyl), wherein preferably the CH₂ group adjacent to the sp² hybridised vinyl carbon atom is replaced.

A fluoroalkyl group is preferably perfluoroalkyl, wherein i is an integer from 1 to 15, in particular CF₃, C₂F₅, C₃F₇, C₄F₉, C₅F₁₁, C₆F₁₃, C₇F₁₅ or C₅F₁₇, very preferably C₆F₁₃, or partially fluorinated alkyl, in particular 1,1-difluoroalkyl, all of which are straight-chain or branched.

Alkyl, alkoxy, alkenyl, oxaalkyl, thioalkyl, carbonyl and carbonyloxy groups can be achiral or chiral groups. Particularly preferred chiral groups are 2-butyl (=1-methylpropyl), 2-methylbutyl, 2-methylpentyl, 3-methylpentyl, 2-ethylhexyl, 2-propylpentyl, in particular 2-methylbutyl, 2-methylbutoxy, 2-methylpentoxy, 3-methylpentoxy, 2-ethyl-hexoxy, 1-methylhexoxy, 2-octyloxy, 2-oxa-3-methylbutyl, 3-oxa-4-methyl-pentyl, 4-methylhexyl, 2-hexyl, 2-octyl, 2-nonyl, 2-decyl, 2-dodecyl, 6-meth-oxyoctoxy, 6-methyloctoxy, 6-methyloctanoyloxy, 5-methylheptyloxy-carbonyl, 2-methylbutyryloxy, 3-methylvaleroyloxy, 4-methylhexanoyloxy, 2-chloropropionyloxy, 2-chloro-3-methylbutyryloxy, 2-chloro-4-methyl-valeryl-oxy, 2-chloro-3-methylvaleryloxy, 2-methyl-3-oxapentyl, 2-methyl-3-oxa-hexyl, 1-methoxypropyl-2-oxy, 1-ethoxypropyl-2-oxy, 1-propoxypropyl-2-oxy, 1-butoxypropyl-2-oxy, 2-fluorooctyloxy, 2-fluorodecyloxy, 1,1,1-trifluoro-2-octyloxy, 1,1,1-trifluoro-2-octyl, 2-fluoromethyloctyloxy for example. Very preferred are 2-hexyl, 2-octyl, 2-octyloxy, 1,1,1-trifluoro-2-hexyl, 1,1,1-trifluoro-2-octyl and 1,1,1-trifluoro-2-octyloxy.

Preferred achiral branched groups are isopropyl, isobutyl (=methylpropyl), isopentyl (=3-methylbutyl), tert-butyl, isopropoxy, 2-methyl-propoxy and 3-methylbutoxy.

In a preferred embodiment, the organyl and organoheteryl groups are independently of each other selected from primary, secondary or tertiary alkyl or alkoxy with 1 to 30 C atoms, wherein one or more H atoms are optionally replaced by F, or aryl, aryloxy, heteroaryl or heteroaryloxy that is optionally alkylated or alkoxylated and has 4 to 30 ring atoms. Very preferred groups of this type are selected from the group consisting of the following formulae

wherein “ALK” denotes optionally fluorinated, preferably linear, alkyl or alkoxy with 1 to 20, preferably 1 to 12 C-atoms, in case of tertiary groups very preferably 1 to 9 C atoms, and the dashed line denotes the link to the ring to which these groups are attached. Especially preferred among these groups are those wherein all ALK subgroups are identical.

—CY¹═CY²— is preferably —CH═CH—, —CF═CF— or —CH═C(CN)—.

As used herein, “halogen” includes F, Cl, Br or I, preferably F, Cl or Br.

For the purposes of the present application the term “substituted” is used to denote that one or more hydrogen present is replaced by a group R^(S) as defined herein.

R^(S) is at each occurrence independently selected from the group consisting of any group R^(T) as defined herein, organyl or organoheteryl having from 1 to 40 carbon atoms wherein the organyl or organoheteryl may be further substituted with one or more groups R^(T) and organyl or organoheteryl having from 1 to 40 carbon atoms comprising one or more heteroatoms selected from the group consisting of N, O, S, P, Si, Se, As, Te or Ge, with N, O, and S being preferred heteroatoms, wherein the organyl or organoheteryl may be further substituted with one or more groups R^(T).

Preferred examples of organyl or organoheteryl suitable as R^(S) may at each occurrence be independently selected from phenyl, phenyl substituted with one or more groups R^(T), alkyl and alkyl substituted with one or more groups R^(T), wherein the alkyl has at least 1, preferably at least 5, more preferably at least 10 and most preferably at least 15 carbon atoms and/or has at most 40, more preferably at most 30, even more preferably at most 25 and most preferably at most 20 carbon atoms. It is noted that for example alkyl suitable as R^(S) also includes fluorinated alkyl, i.e. alkyl wherein one or more hydrogen is replaced by fluorine, and perfluorinated alkyl, i.e. alkyl wherein all of the hydrogen are replaced by fluorine.

R^(T) is at each occurrence independently selected from the group consisting of F, Br, Cl, —CN, —NC, —NCO, —NCS, —OCN, —SCN, —C(O)NR⁰R⁰⁰, —C(O)X⁰, —C(O)R⁰, —NH₂, —NR⁰R⁰⁰, —SH, —SR⁰, —SO₃H, —SO₂R⁰, —OH, —OR⁰, —NO₂, —SF₅ and —SiR⁰R⁰⁰R⁰⁰⁰. Preferred R^(T) are selected from the group consisting of F, Br, Cl, —CN, —NC, —NCO, —NCS, —OCN, —SCN, —C(O)NR⁰R⁰⁰, —C(O)X⁰, —C(O)R⁰, —NH₂, —NR⁰R⁰⁰, —SH, —SR⁰, —OH, —OR and —SiR⁰R⁰⁰R⁰⁰⁰.

R⁰, R⁰⁰ and R⁰⁰⁰ are at each occurrence independently of each other selected from the group consisting of H, F, organyl or organoheteryl having from 1 to 40 carbon atoms. Said organyl or organoheteryl preferably have at least 5, more preferably at least 10 and most preferably at least 15 carbon atoms. Said organyl or organoheteryl preferably have at most 30, even more preferably at most 25 and most preferably at most 20 carbon atoms. Preferably, R⁰, R⁰⁰ and R⁰⁰⁰ are at each occurrence independently of each other selected from the group consisting of H, F, alkyl, fluorinated alkyl, alkenyl, alkynyl, phenyl and fluorinated phenyl. More preferably, R⁰, R⁰⁰ and R⁰⁰⁰ are at each occurrence independently of each other selected from the group consisting of H, F, alkyl, fluorinated, preferably perfluorinated, alkyl, phenyl and fluorinated, preferably perfluorinated, phenyl.

It is noted that for example alkyl suitable as R⁰, R⁰⁰ and R⁰⁰⁰ also includes perfluorinated alkyl, i.e. alkyl wherein all of the hydrogen are replaced by fluorine. Examples of alkyls may be selected from the group consisting of methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl (or “t-butyl”), pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl (—C₂₀H₄₁).

X⁰ is halogen. Preferably X⁰ is selected from the group consisting of F, Cl and Br.

The present application relates to a formulation comprising a polymer which comprises a first repeating unit U¹ and a second repeating unit U²; and surface-modified nanoparticles, wherein the surface-modified nanoparticles do not contain any zirconium dioxide.

In a preferred embodiment the polymer comprises at least one further repeating unit U¹ which is different from the first repeating unit U¹. If the polymer comprises more than one further repeating unit U¹, such further repeating units U¹ are mutually different from each other. More preferably, the polymer comprises two, three or four further repeating units U¹ which are different from the first repeating unit U¹ and which are mutually different from each other.

In a preferred embodiment the polymer comprises at least one further repeating unit U² which is different from the second repeating unit U². If the polymer comprises more than one further repeating unit U², such further repeating units U² are mutually different from each other. More preferably, the polymer comprises two, three or four further repeating units U² which are different from the second repeating unit U² and which are mutually different from each other.

In a more preferred embodiment the polymer comprises at least one further repeating unit U¹ and at least one further repeating unit U² as defined above.

Preferably, the polymer is a copolymer such as a random copolymer or a block copolymer or a copolymer containing at least one random sequence section and at least one block sequence section. More preferably, the polymer is a random copolymer or a block copolymer.

Said first repeating unit U¹ is represented by formula (I):

—[SiR¹R²—NR⁵—]—  (I)

wherein R¹, R² and R⁵ are as defined herein.

Said second repeating unit U² is represented by formula (II):

—[—SiR³R⁴—[—O—SiR³R⁴—]_(a)—NR⁵—]—  (II)

wherein R³, R⁴ and R⁵ and the index “a” are as defined herein.

Said further repeating unit U¹ is represented by formula (I), wherein the further repeating unit U¹ is different from the first repeating unit U¹.

a is an integer from 1 to 60, preferably an integer from 1 to 50. More preferably, a may be an integer from 40 to 50 (long chain monomer M²), even more preferably any one of the group consisting of 40, 41, 42, 43, 44, 45, 46, 47, 48, 49 and 50, or a may be an integer from 1 to 4 (short chain monomer M²), even more preferably any one of the group consisting of 1, 2, 3 and 4.

R¹, R², R³, R⁴ and R⁵ are at each occurrence independently from each other selected from the group consisting of hydrogen, organyl and organoheteryl groups.

Preferred organyl groups may at each occurrence independently be selected from the group consisting of alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, alkenyl, substituted alkenyl, alkadienyl, substituted alkadienyl, alkinyl, substituted alkinyl, aryl, and substituted aryl.

More preferred organyl groups may at each occurrence independently be selected from the group consisting of alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, alkenyl, substituted alkenyl, alkadienyl and substituted alkadienyl.

Even more preferred organyl groups may at each occurrence independently be selected from the group consisting of alkyl, substituted alkyl, alkenyl, substituted alkenyl, alkadienyl and substituted alkadienyl.

Still even more preferred organyl groups may at each occurrence independently be selected from the group consisting of alkyl and substituted alkyl.

Most preferred organyl groups may at each occurrence independently be selected from the group consisting of alkyl.

Preferred alkyl may be selected from alkyls having at least 1 carbon atom and at most 40 carbon atoms, preferably at most 30 or 20 carbon atoms, more preferably at most 15 carbon atoms, still even more preferably at most 10 carbon atoms and most preferably at most 5 carbon atoms.

Alkyl having at least 1 carbon atom and at most 5 carbon atoms may, for example, independently be selected from the group consisting of methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, n-pentyl, iso-pentyl (2,2-methyl-butyl) and neo-pentyl (2,2-dimethyl-propyl); preferably from the group consisting of methyl, ethyl, n-propyl and iso-propyl; more preferably is methyl or ethyl; and most preferably is methyl.

Preferred cycloalkyl may be selected from cycloalkyl having at least 3, preferably at least 4 and most preferably at least 5 carbon atoms. With respect to R¹ and R² preferred cycloalkyl may be selected from cycloalkyl having at most 30, preferably at most 25, more preferably at most 20, even more preferably at most 15, and most preferably at most 10 carbon atoms.

Preferred examples of cycloalkyl may be selected from the group consisting of cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl.

Preferred alkenyl may be selected from alkenyl having at least 2 carbon atoms and at most 20, more preferably at most 15, even more preferably at most 10, and most preferably at most 6 carbon atoms. Said alkenyl may comprise the C═C double bond at any position within the molecule; for example, the C═C double bond may be terminal or non-terminal.

Alkenyl having at least 2 and at most 10 carbon atoms may be vinyl or allyl, preferably vinyl.

Preferred alkadienyl may be selected from alkadienyl having at least 4 and at most 20, more preferably at most 15, even more preferably at most 10, and most preferably at most 6 carbon atoms. Said alkenyl may comprise the two C═C double bonds at any position within the molecule, provided that the two C═C double bonds are not adjacent to each other; for example, the C═C double bonds may be terminal or non-terminal.

Alkadienyl having at least 4 and at most 6 carbon atoms may, for example, be butadiene or hexadiene.

Preferred aryl may be selected from aryl having at least 6 carbon atoms, and at most 30, preferably at most 24 carbon atoms.

Preferred examples of aryl may be selected from the group consisting of phenyl, naphthyl, phenanthrenyl, anthracenyl, tetracenyl, benz[a]anthracenyl, pentacenyl, chrysenyl, benzo[a]pyrenyl, azulenyl, perylenyl, indenyl, fluorenyl and any of these wherein one or more (for example 2, 3 or 4) CH groups are replaced by N. Of these phenyl, naphthyl and any of these wherein one or more (for example 2, 3 or 4) CH groups are replaced by N. Phenyl is most preferred.

In a preferred embodiment, R¹ and R² are at each occurrence independently from each other hydrogen or alkyl having 1 to 20 carbon atoms or phenyl.

In a more preferred embodiment, R¹ and R² are at each occurrence independently from each other hydrogen or methyl.

In a preferred embodiment, R³ and R⁴ are independently from each other hydrogen or alkyl having 1 to 40 carbon atoms or phenyl.

In a more preferred embodiment, R³ and R⁴ are independently from each other methyl or phenyl.

In a preferred embodiment, R⁵ is at each occurrence independently hydrogen or alkyl having 1 to 20 carbon atoms or phenyl.

In a more preferred embodiment, R⁵ is at each occurrence independently hydrogen or methyl.

It is understood that the skilled person can freely combine the above-mentioned preferred and more preferred embodiments relating to the substituents R¹, R², R³, R⁴ and R⁵ in the polymer comprising the first repeating unit U¹ and the second repeating unit U² in any desired way.

Preferably, the poylmers used in the present invention have a molecular weight M_(w), as determined by GPC, of at least 1,000 g/mol, more preferably of at least 2,000 g/mol, even more preferably of at least 3,000 g/mol. Preferably, the molecular weight M_(w) of the polymers is less than 100,000 g/mol. More preferably, the molecular weight M_(w) of the polymers is in the range from 3,000 to 50,000 g/mol.

If necessary, the molecular weight of the polymers may be modified, preferably increased, by fluoride-catalyzed crosslinking or by base-catalyzed crosslinking. These methods are well known to the skilled person.

The present polymers are characterized by an excellent temperature resistance and/or longevity as compared to currently used standard materials, such as phenylsilicone or organopolysilazanes.

The surface-modified nanoparticles which do not contain any zirconium dioxide are surface-modified nanoparticles which are free of any zirconium dioxide.

Preferably, the surface-modified nanoparticles which do not contain any zirconium dioxide are inorganic particles which are modified on their surface with a surface-modifying agent.

In a preferred embodiment the surface-modified nanoparticles which do not contain any zirconium dioxide are surface-modified nanoparticles containing one or more inorganic nanoparticle materials selected from M²O, M³ ₂O₃, M^(4a)O₂, M²M^(4b)O₃, M²S, M²SO₃, M²SO₄, M² ₂SiO₄, M³N, M^(4b)C, M^(4b)SiO₄ and diamond, wherein M² is a divalent metal element, M³ is a trivalent metal element, M^(4a) is a tetravalent metal element excluding Zr and M^(4b) is a tetravalent metal element.

Preferably, M² is a divalent metal element selected from the list consisting of Mg, Ca, Sr, Ba, Cr, Mn, Fe, Co, Ni, Cu, Zn, Cd, Hg, Sn and Pb; M³ is a trivalent metal element selected from the list consisting of Sc, Y, Lu, Cr, Mn, Fe, B, Al and Ga; M^(4a) is a tetravalent metal element excluding Zr selected from the list consisting of Ti, Hf, Si, Ge and Sn; and M^(4b) is a tetravalent metal element selected from the list consisting of Ti, Zr, Hf, Si, Ge and Sn.

More preferably, M² is a divalent metal element selected from the list consisting of Mg, Ca, Sr, Ba, Fe, Zn and Pb; M³ is a trivalent metal element selected from the list consisting of Fe, B, Al and Ga; M^(4a) is a tetravalent metal element excluding Zr selected from the list consisting of Ti, Hf and Si; and M^(4b) is a tetravalent metal element selected from the list consisting of Ti, Zr, Hf and Si.

Most preferably, M² is a divalent metal element selected from the list consisting of Zn and Pb; M³ is a trivalent metal element selected from the list consisting of Fe and Al; M^(4a) is a tetravalent metal element excluding Zr selected from the list consisting of Ti and Si; and M^(4b) is a tetravalent metal element selected from the list consisting of Ti, Zr and Si.

Particularly preferred inorganic nanoparticle materials for the preparation of surface-modified nanoparticles to be used in the formulation according to the present invention are given in Table 1 below. The examples shown in Table 1 are for illustrative purposes only and should not be construed as limiting. Suitable inorganic nanoparticle materials are e.g. nitrides, titanates, diamond, oxides, sulfides, sulfites, sulfates, silicates and carbides.

TABLE 1 Particularly preferred inorganic nanoparticle materials for the preparation of surface-modified nanoparticles and their refractive indices (RI). Inorganic Nanoparticle Material Refractive Index (RI) Aluminum nitride [AIN] 2.2 Barium titanate [BaTiO₃] 2.4 Diamond [C] 2.4 Iron oxide [Fe₂O₃] 2.9 Lead sulfide [PbS] 3.9 Silicon carbide [SiC] 2.6 Titanium dioxide (anatas) [TiO₂] 2.5 Titanium dioxide (rutile) [TiO₂] 2.9

Generally, the refractive index (RI) of a homogeneous material can be increased by addition of nanoparticles having a higher RI as the base material itself. If the surface-modified nanoparticles are small enough and homogeneously dispersed in the base material, the RI of the hybrid material is an average of both RIs. The inorganic nanoparticle materials shown in Table 1 are well known to have high refractive indices and are available as nanoparticles.

The inorganic nanoparticles as used herein are particles with a diameter of <100 nm, preferably ≤95 nm, more preferably ≤90 nm, even more preferably ≤85 nm, even more preferably ≤80 nm, even more preferably ≤75 nm, even more preferably ≤70 nm, even more preferably ≤65 nm, even more preferably ≤60 nm, even more preferably ≤55 nm, even more preferably ≤50 nm, even more preferably ≤45 nm, even more preferably ≤40 nm, even more preferably ≤35 nm, even more preferably ≤30 nm, even more preferably ≤25 nm, and most preferably ≤20 nm.

If the diameter of the nanoparticles is >100 nm, the formulation gets opaque or turbid. Thus, it is preferred that the diameter of the inorganic nanoparticle materials in Table 1 is such that the diameter of the surface-modified nanoparticles prepared therefrom is <100 nm, preferably ≤95 nm, more preferably ≤90 nm, even more preferably ≤85 nm, even more preferably ≤80 nm, even more preferably ≤75 nm, even more preferably ≤70 nm, even more preferably ≤65 nm, even more preferably ≤60 nm, even more preferably ≤55 nm, even more preferably ≤50 nm, even more preferably ≤45 nm, even more preferably ≤40 nm, even more preferably ≤35 nm, even more preferably ≤30 nm, even more preferably ≤25 nm, and most preferably ≤20 nm.

Preferably, the inorganic nanoparticle materials used for the preparation of the surface-modified nanoparticles have a RI of ≥2.

Preferably, the surface-modified nanoparticles used in the formulation according to the present invention are modified on their surface with a surface-modifying agent, more preferably an organic surface-modifying agent. Such surface-modifying agents provide a surface coating, preferably an organic surface coating, which covers the surface of the inorganic nanoparticle material. Such surface-modified nanoparticles allow the preparation of homogeneous dispersions in siloxazane polymer formulations. The surface-modification is necessary to obtain a stable dispersion of nanoparticles in organic solvents without agglomeration or precipitation and to avoid reaction or agglomeration with the siloxazane polymer.

Preferably, the surface of the nanoparticles is modified with surface modifying agents selected from alkyl-alkoxysilanes, alkenyl-alkoxysilanes or aryl-alkoxysilanes. Such alkyl-alkoxysilanes, alkenyl-alkoxysilanes or aryl-alkoxysilanes react with binding sites on the surface of the inorganic nanoparticle material and form covalent bonds to the binding sites on the surface of the inorganic nanoparticle material.

Particularly preferred alkyl-alkoxysilanes, alkenyl-alkoxysilanes and aryl-alkoxysilanes are represented by RSi(OR′)₃, R₂Si(OR′)₂ or R₃Si(OR′)₁, wherein R and R′ may be the same or different on each occasion and are independently selected from the group consisting of hydrogen, straight-chain alkyl groups having from 1 to 20 carbon atoms, straight-chain alkenyl groups having from 2 to 20 carbon atoms, branched-chain alkyl or alkenyl groups having from 3 to 20 carbon atoms, cyclic alkyl or alkenyl groups having from 3 to 20 carbon atoms, and aryl or heteroaryl groups having from 4 to 6 carbon atoms, wherein one or more hydrogen atoms may be optionally replaced by F.

More preferably, R is selected on each occasion independently from the group consisting of hydrogen, methyl, ethyl, 1-propyl, 2-propyl, n-butyl, iso-butyl, sec-butyl, t-butyl, n-pentyl, 2-pentyl, 3-pentyl, 2-methylbutyl, 3-methylbutyl, 3-methylbut-2-yl, 2-methylbut-2-yl, 2,2-dimethylpropyl, n-hexyl, 2-hexyl, 3-hexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 2-methylpent-2-yl, 3-methylpent-2-yl, 2-methylpent-3-yl, 3-methylpent-3-yl, 2-ethylbutyl, 3-ethylbutyl, 2,3-dimethylbutyl, 2,3-dimethylbut-2-yl, 2,2-dimethylbutyl, n-heptyl, n-octyl, iso-octyl, n-nonyl and n-decyl, n-dodecyl, n-hexadecyl, n-octadecyl, vinyl, allyl, 1-butenyl, 1-pentenyl, 1-hexenyl, 1-heptenyl, 1-octenyl and phenyl; and R′ is selected on each occasion independently from the group consisting of methyl and ethyl.

Particularly preferred alkyl-alkoxysilanes are e.g. methyl-trimethoxysilane, methyl-triethoxysilane, trimethyl-methoxysilane, trimethyl-ethoxysilane, ethyl-trimethoxysilane, ethyl-triethoxysilane, triethyl-methoxysilane, triethyl-ethoxysilane, propyl-trimethoxysilane, propyl-triethoxysilane, tripropyl-methoxysilane, tripropyl-ethoxysilane, n-hexyl-trimethoxysilane and n-hexyl-triethoxysilane.

Particularly preferred alkenyl-alkoxysilanes are e.g. vinyl-trimethoxysilane, vinyl-triethoxysilane, trivinyl-methoxysilane, trivinyl-ethoxysilane, allyl-trimethoxysilane, allyl-triethoxysilane, triallyl-methoxysilane and triallyl-ethoxysilane.

Particularly preferred aryl-alkxoysilanes are e.g. phenyl-trimethoxysilane and phenyl-triethoxysilane.

Well known techniques for modifying the surface of nanoparticles with alkyl-alkoxysilanes, alkenyl-alkoxysilanes and/or phenyl-alkoxysilanes are described for example in US 2008/0317794 A1, US 2005/0154124 A1 and J. Mater. Chem., 2009, 19, 2884-2901. Typically, a mixture of short and long chained silanes is used to fully cover the nanoparticles' surface and to avoid aggregation by mutual repulsion of the long alkyl chains.

Advantageously, the nanoparticles are directly used as a dispersion. In case the nanoparticles are available as a solid only, they first have to be dispersed in water or in any other suitable solvent which may be a non-polar or polar non-protic solvent, preferably an organic solvent.

Preferred examples of suitable organic solvents for the nanoparticle dispersion may be selected from the group consisting of ethers, cyclic ethers, ketones, esters, mixed ether/ester solvents, hydrocarbons, aromatic solvents and any mixture of any of these, wherein one or more hydrogen atoms in the solvent may be optionally substituted by chlorine or fluorine atoms.

Preferred examples of ethers are methyl-tert-butylether, di-ethylether, methyl-isobutylether, methyl-isopropylether, di-n-propylether, di-isopropylether, methyl-cyclopentylether, all isomers of di-butyl- and di-pentylether and polyethers like ethylenglycol-dimethylether, ethylenglycol-diethylether, propylenglycol-dimethylether, propylenglycol-diethylether, diethylenglycol-dimethyl ether and dipropylenglycol-dimethyl ether.

Preferred examples of cyclic ethers are tetrahydrofuran (THF), 2-methyl-tetrahydrofuran, 1,3-dioxolan, tetrahydropyran and 1,4-dioxan.

Preferred examples of ketones are acetone, methyl-ethyl-ketone, methyl-isobutyl-ketone, 2- or 3-, n- or iso-pentanon, cyclopentanone, cyclohexanone, n- or iso-, 2- or 3-hexanone, n- or iso-, 2- ,3- or 4-heptanone.

Preferred examples of esters are methyl-acetate, ethyl-acetate, propyl-acetate, n-butyl-acetate, iso-butyl-acetate, tert-butyl acetate, adipic acid dimethyl ester, methyl-benzoate, dimethylsuccinate and cyclic esters like γ-butyrolactone and γ- or ε-valerolactone.

Preferred examples of mixed ether/ester solvents are 2-methoxy-propyl acetate (PGMEA), butyl glycol acetate, ethylenglycol-methylether-acetat and ethylenglycol-ethyleter-acetat.

Preferred examples of hydrocarbons are linear hydrocarbons like pentane, hexane, heptane, octane, nonane, decane and the branched isomers like for example iso-octane and cyclic hydrocarbons like cyclopentane, cyclo hexane and decalin and mixtures for example known under the trivial names benzine, petrolether, white spirit and mineral spirit available for example under the trade names Shellsol® and Isopar®.

Preferred examples of aromatic solvents may be selected from the group consisting of benzene, toluene, ortho-xylene, meta-xylene, para-xylene, chloro benzene, dichloro benzene, anisol and methyl anisol and any mixture of any of these.

As described above, the surface-modified nanoparticles are advantageously used as a dispersion in water or any other suitable solvent which may be a non-polar or polar non-protic solvent, preferably an organic solvent.

It is therefore preferred that the formulation of the present invention further contains one or more suitable solvents. A suitable solvent comprised in said formulation comprising the polymer and the surface-modified nanoparticles is not particularly limited provided that the components of said formulation have a sufficient solubility therein. Preferably, said suitable solvent may be a non-polar or polar non-protic solvent, preferably an organic solvent.

Preferred examples of suitable organic solvents for the formulation may be selected from the group consisting of ethers, cyclic ethers, ketones, esters, mixed ether/ester solvents, hydrocarbons, aromatic solvents and any mixture of any of these, wherein one or more hydrogen atoms in the solvent may be optionally substituted by chlorine or fluorine atoms.

Preferred examples of ethers are methyl-tert-butylether, di-ethylether, methyl-isobutylether, methy-isopropylether, di-n-propylether, di-isopropylether, methyl-cyclopentylether, all isomers of di-butyl- and di-pentylether and polyethers like ethylenglycol-dimethylether, ethylenglycol-diethylether, propylenglycol-dimethylether, propylenglycol-diethylether, diethylenglycol-dimethyl ether and dipropylenglycol-dimethyl ether.

Preferred examples of cyclic ethers are tetrahydrofuran (THF), 2-methyl-tetrahydrofuran, 1,3-dioxolan, tetrahydropyran and 1,4-dioxan.

Preferred examples of ketones are acetone, methyl-ethyl-ketone, methyl-isobutyl-ketone, 2- or 3-, n- or iso-pentanon, cyclopentanone, cyclohexanone, n- or iso-, 2- or 3-hexanone, n- or iso-, 2- ,3- or 4-heptanone.

Preferred examples of esters are methyl-acetate, ethyl-acetate, propyl-acetate, n-butyl-acetate, iso-butyl-acetate, tert-butyl acetate, adipic acid dimethyl ester, methyl-benzoate, dimethylsuccinate and cyclic esters like γ-butyrolactone and γ- or ε-valerolactone.

Preferred examples of mixed ether/ester solvents are 2-methoxy-propyl acetate (PGMEA), butyl glycol acetate, ethylenglycol-methylether-acetat and ethylenglycol-ethyleter-acetat.

Preferred examples of hydrocarbons are linear hydrocarbons like pentane, hexane, heptane, octane, nonane, decane and the branched isomers like for example iso-octane and cyclic hydrocarbons like cyclopentane, cyclo hexane and decalin and mixtures for example known under the trivial names benzine, petrolether, white spirit and mineral spirit available for example under the trade names Shellsol® and Isopar®.

Preferred examples of aromatic solvents may be selected from the group consisting of benzene, toluene, ortho-xylene, meta-xylene, para-xylene, chloro benzene, dichloro benzene, anisol and methyl anisol and any mixture of any of these.

The solvent(s) used in the formulation are chosen or modified such that they fit to the respective application method which is used to apply the formulation of the invention to an LED.

Preferably, the total content of the polymer and the surface-modified nanoparticles in the formulation is in the range from 5 to 99 weight % depending on the respective application method which is used for applying the formulation of the present application to an LED. The formulation of the invention may be applied by any known application method such as, for example, dispensing, screen printing, stencile printing, spray coating, slot coating and other methods such as spin coating and ink-jet printing.

For example, it is preferred that the total content of the polymer and the surface-modified nanoparticles is in the range from 70 to 99.9 weight %, more preferably from 90 to 99.9 weight %, if dispensing is used.

For example, it is preferred that the total content of the polymer and the surface-modified nanoparticles is in the range from 50 to 99.9 weight %, more preferably from 70 to 99.9 weight %, if screen printing or stencile printing is used.

For example, it is preferred that the total content of the polymer and the surface-modified nanoparticles is in the range from 5 to 30 weight %, more preferably from 5 to 25 weight %, and most preferably from 5 to 20 weight %, if spray coating is used.

For example, it is preferred that the total content of the polymer and the surface-modified nanoparticles is in the range from 50 to 99.9 weight %, more preferably from 70 to 99 weight %, if slot coating is used.

For example, it is preferred that the total content of the polymer and the surface-modified nanoparticles is in the range from 5 to 90 weight %, more preferably from 20 to 80 weight %, if spin coating is used.

For example, it is preferred that the total content of the polymer and the surface-modified nanoparticles is in the range from 5 to 99 weight %, more preferably from 20 to 95 weight %, if ink-jet printing is used.

For example, if spray coating is used, a preferred solvent system comprises a solvent A) with a boiling point of <90° C. and a solvent B) with a boiling point of >90° C. The low boiling solvent A) is preferably an ester, an ether and/or a ketone solvent and the high boiling solvent B) is preferably an ester, an ether, an alkane and/or an aromatic solvent.

Furthermore, a method for preparing a formulation of the present invention is provided, wherein the polymer containing a first repeating unit U¹ and a second repeating unit U² as defined above is mixed with a dispersion of surface-modified nanoparticles, wherein the surface-modified nanoparticles do not contain any zirconium dioxide. In said dispersion the surface-modified nanoparticles are dispersed in a liquid which may be water or any other suitable solvent as described above.

Furthermore, it is preferred that the polymer is provided in the form of a solution. Regarding the solvent for the polymer there are no specific restrictions as long as the solvent is able to solve the polymer in a sufficient amount. Typically, the polymer is dissolved in a suitable solvent which is identical or similar to or at least compatible with the liquid in which the surface-modified nanoparticles are dispersed.

Preferred examples of suitable solvents for the polymer may be selected from the group consisting of water, ethers, cyclic ethers, ketones, esters, mixed ether/ester solvents, hydrocarbons, aromatic solvents and any mixture of any of these, wherein one or more hydrogen atoms in the solvent may be optionally substituted by chlorine or fluorine atoms.

Preferred examples of ethers are methyl-tert-butylether, di-ethylether, methyl-isobutylether, methy-isopropylether, di-n-propylether, di-isopropylether, methyl-cyclopentylether, all isomers of di-butyl- and di-pentylether and polyethers like ethylenglycol-dimethylether, ethylenglycol-diethylether, propylenglycol-dimethylether, propylenglycol-diethylether, diethylenglycol-dimethyl ether and dipropylenglycol-dimethyl ether.

Preferred examples of cyclic ethers are tetrahydrofuran (THF), 2-methyl-tetrahydrofuran, 1,3-dioxolan, tetrahydropyran and 1,4-dioxan.

Preferred examples of ketones are acetone, methyl-ethyl-ketone, methyl-isobutyl-ketone, 2- or 3-, n- or iso-pentanon, cyclopentanone, cyclohexanone, n- or iso-, 2- or 3-hexanone, n- or iso-, 2- ,3- or 4-heptanone.

Preferred examples of esters are methyl-acetate, ethyl-acetate, propyl-acetate, n-butyl-acetate, iso-butyl-acetate, tert-butyl acetate, adipic acid dimethyl ester, methyl-benzoate, dimethylsuccinate and cyclic esters like γ-butyrolactone and γ- or ε-valerolactone.

Preferred examples of mixed ether/ester solvents are 2-methoxy-propyl acetate (PGMEA), butyl glycol acetate, ethylenglycol-methylether-acetat and ethylenglycol-ethyleter-acetat.

Preferred examples of hydrocarbons are linear hydrocarbons like pentane, hexane, heptane, octane, nonane, decane and the branched isomers like for example iso-octane and cyclic hydrocarbons like cyclopentane, cyclo hexane and decalin and mixtures for example known under the trivial names benzine, petrolether, white spirit and mineral spirit available for example under the trade names Shellsol® and Isopar®.

Preferred examples of aromatic solvents may be selected from the group consisting of benzene, toluene, ortho-xylene, meta-xylene, para-xylene, chloro benzene, dichloro benzene, anisol and methyl anisol and any mixture of any of these.

The solvent(s) used for preparing the formulation are chosen or modified such that they are suitable for the respective application method which is used to apply the formulation of the invention to an LED precursor. For example, during evaporation of the solvent and the simultaneous film formation, the dispersibility of the surface-modified nanoparticles should not decrease and no agglomeration of the material should occur, which may form particle-like structures preventing the coating from being transparent to visible light. Good coating results and reliable data are achieved by using solvents such as ethers, esters, ketones, hydrocarbons and aromatic solvents.

Preferably, the formulation may comprise one or more additives selected from the group consisting of converters, viscosity modifiers, surfactants, additives influencing film formation, additives influencing evaporation behavior and cross-linkers. Most preferably, said formulation further comprises a converter.

In a preferred embodiment a dispersion of the surface-modified nanoparticles is added to a solution of the polymer and then mixed. As an alternative to this preferred embodiment a solution of the polymer may be added to a dispersion of the surface-modified nanoparticles and then mixed.

It is preferred that the formulation of the invention is prepared at ambient temperature, i.e. 25° C., however, it may also be prepared at elevated temperatures.

In addition, an encapsulation material for an LED is provided, wherein the encapsulation material is obtainable by

-   -   (a) providing a formulation according to the invention; and     -   (b) curing said formulation at a temperature of 70 to 300° C.         for a period of 1 to 24 h.

It is preferred that the curing in step (b) is carried out on a hot plate, in a furnace, or in a climate chamber.

Preferably, the curing in step (b) is carried out on a hot plate at a temperature of 100 to 280° C., more preferably from 120 to 270° C., and most preferably from 150 to 250° C.

In an alternative preferred embodiment, the curing in step (b) is carried out in a furnace at a temperature of 100 to 280° C., more preferably from 120 to 270° C., and most preferably from 150 to 250° C.

In an alternative preferred embodiment, the curing in step (b) is carried out in a climate chamber having a relative humidity in the range from 50 to 99%, more preferably from 60 to 95%, and most preferably from 80 to 90%, at a temperature of 70 to 95° C., more preferably from 80 to 90° C.

Preferably, the curing time is from 2 to 20 h, more preferably from 3 to 18 h, and most preferably from 4 to 16 h, depending on the application thickness, the monomer composition of the polymer, and the curing method.

There is further provided an LED comprising the encapsulation material of the present invention. Particular preference is given here to an LED comprising a semiconductor light source (LED chip) and at least one converter, preferably a phosphor or quantum material. The LED is preferably white-emitting or emits light having a certain colour point (colour-on-demand principle). The colour-on-demand concept is taken to mean the production of light having a certain colour point using a pc-LED (=phosphor-converted LED) using one or more phosphors.

In a preferred embodiment of the LED according to the invention, the semiconductor light source (LED chip) is a luminescent indium aluminium gallium nitride, in particular of the formula In_(i)Ga_(j)Al_(k)N, where 0≤i, 0≤j, 0≤k, and i+j+k=1. These can be light-emitting LED chips of various structure.

In a further preferred embodiment of the LED according to the invention, the LED is a luminescent arrangement based on ZnO, TCO (transparent conducting oxide), ZnSe or SiC.

In a further preferred embodiment of the light source according to the invention, the LED is a light source which exhibits electroluminescence and/or photoluminescence.

It is preferred that the encapsulation material of the invention is comprised in a converter layer of the LED. Preferably, the converter layer contains the encapsulation material and a converter, more preferably a phosphor and/or a quantum material. The converter layer is either arranged directly on the semiconductor light source (LED chip) or alternatively arranged remote therefrom, depending on the respective type of application (the latter arrangement also includes “remote phosphor technology”). The advantages of remote phosphor technology are known to the person skilled in the art and are revealed, for example, by the following publication: Japanese J. of Appl. Phys. Vol. 44, No. 21 (2005), L649-L651.

The optical coupling between the semiconductor light source (LED chip) and the converter layer can also be achieved by a light-conducting arrangement. This makes it possible for the semiconductor to be installed at a central location and to be optically coupled to the converter layer by means of light-conducting devices, such as, for example, optical fibres. In this way, it is possible to achieve lamps adapted to the lighting wishes which merely consist of one or various phosphors, which can be arranged to form a light screen, and an optical waveguide, which is coupled to the light source. In this way, it is possible to place a strong light source at a location which is favourable for electrical installation and to install lamps comprising phosphors which are coupled to the optical waveguides at any desired locations without further electrical cabling, but instead only by laying optical wave-guides.

Preferably, the converter is a phosphor, i.e. a substance having luminescent properties. The term “luminescent” is intended to include both, phosphorescent as well as fluorescent.

For the purposes of the present application, the type of phosphor is not particularly limited. Suitable phosphors are well known to the skilled person and can easily be obtained from commercial sources. For the purposes of the present application the term “phosphor” is intended to include materials that absorb in one wavelength of the electromagnetic spectrum and emit at a different wavelength.

Examples of suitable phosphors are inorganic fluorescent materials in particle form comprising one or more emitting centers. Such emitting centers may, for example, be formed by the use of so-called activators, which are preferably atoms or ions selected from the group consisting of rare earth elements, transition metal elements, main group elements and any combination of any of these. Example of suitable rare earth elements may be selected from the group consisting of La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu. Examples of suitable transition metal elements may be selected from the group consisting of Cr, Mn, Fe, Co, Ni, Cu, Ag, Au and Zn. Examples of suitable main group elements may be selected from the group consisting of Na, TI, Sn, Pb, Sb and Bi. Examples of suitable phosphors include phosphors based on garnet, silicate, orthosilicate, thiogallate, sulfide, nitride, silicon-based oxynitride, nitridosilicate, nitridoaluminiumsilicate, oxonitridosilicate, oxonitridoaluminiumsilicate and rare earth doped sialon.

Suitable yellow phosphors may, for example, comprise or be based on (Gd, Y)₃(Al, Ga)₅O₁₂ doped with Ce, such as the commercially available cerium-doped yttrium aluminium garnet (frequently abbreviated as “Ce:YAG” or “YAG:Ce”); or Th_(3-x)M_(x)X₁₂:Ce (TAG) with M being selected from the group consisting of Y, Gd, La and Lu; or Sr_(2-x-y)Ba_(x)Ca_(y)SiO₄:Eu.

Examples of green phosphors may be selected from the group of SrGa₂S₄:Eu; Sr_(2-y)Ba_(y)SiO₄:Eu and/or SrSi₂O₂N₂:Eu.

Phosphors which may be employed as converter in the converting layer of the LED are, for example: Ba₂SiO₄:Eu²⁺, BaSi₂O₅:Pb²⁺, Ba_(x)Sr_(1-x)F₂:Eu₂₊, BaSrMgSi₂O₇:Eu²⁺, BaTiP₂O₇, (Ba, Ti)₂P₂O₇:Ti, Ba₃WO₆:U, BaY₂F₈:Er³⁺, Yb⁺, Be₂SiO₄:Mn²⁺, Bi₄Ge₃O₁₂, CaAl₂O₄:Ce³⁺, CaLa₄O₇:Ce³⁺, CaAl₂O₄:Eu²⁺, CaAl₂O₄:Mn²⁺, CaAl₄O₇:Pb²⁺, Mn²⁺, CaAl₂O₄:Tb³⁺, Ca₃Al₂Si₃O₁₂:Ce³⁺, Ca₃Al₂Si₃O₁₂:Eu²⁺, Ca₂B₆O₉BrEu²⁺, Ca₂B₅O₉Cl:Eu²⁺, Ca₂B₅O₉C:Pb²⁺, CaB₂O₄:Mn²⁺, Ca₂B₂O₆:Mn²⁺, CaB₂O₄:Pb²⁺, CaB₂P₂O₉:Eu²⁺, Ca₅B₂SiO₁₀:Eu³⁺, Ca_(0.5)Ba_(0.5)Al₁₂O₁₉:Ce³⁺, Mn²⁺, Ca₂Ba₃(PO₄)₃Cl:Eu²⁺, CaBr₂:Eu²⁺ in SiO₂, CaCl₂:Eu²⁺ in SiO₂, CaCl₂:Eu²⁺, Mn²⁺ in SiO₂, CaF₂:Ce³⁺, CaF₂:Ce³⁺, Mn²⁺, CaF₂:Ce³⁺, Tb³⁺, CaF₂:Eu²⁺, CaF₂:Mn²⁺, CaF₂:U, CaGa₂O₄:Mn²⁺, CaGa₄O₇:Mn²⁺, CaGa₂S₄:Ce³⁺, CaGa₂S₄:Eu²⁺, CaGa₂S₄:Mn²⁺, CaGa₂S₄:Pb²⁺, CaGeO₃:Mn²⁺, CaI₂:Eu²⁺ in SiO₂, CaI₂:Eu²⁺, Mn²⁺ in SiO₂, CaLaBO₄:Eu³⁺, CaLaB₃O₇:Ce³⁺, Mn²⁺, Ca₂La₂BO_(6.5):Pb²⁺, Ca₂MgSi₂O₇, Ca₂MgSi₂O₇:Ce³⁺, CaMgSi₂O₆:Eu²⁺, Ca₃MgSi₂O₈:Eu²⁺, Ca₂MgSi₂O₇:Eu²⁺, CaMgSi₂O₆:Eu²⁺, Mn²⁺, Ca₂MgSi₂O₇:Eu²⁺, Mn²⁺, CaMoO₄, CaMoO₄:Eu³⁺, CaO:Bi³⁺, CaO:Cd²⁺, CaO:Cu⁺, CaO:Eu³⁺, CaO:Eu³⁺, Na⁺, CaO:Mn²⁺, CaO:Pb²⁺, CaO:Sb³⁺, CaO:Sm³⁺, CaO:Tb³⁺, CaO:TI, CaO:Zn²⁺, Ca₂P₂O₇:Ce³⁺, α-Ca₃(PO₄)₂:Ce³⁺, β-Ca₃(PO₄)₂:Ce³⁺, Ca₆(PO₄)₃Cl:Eu²⁺, Ca₆(PO₄)₃Cl:Mn²⁺, Ca₆(PO₄)₃Cl:Sb³⁺, Ca₆(PO₄)₃Cl:Sn²⁺, β-Ca₃(PO₄)₂:Eu²⁺, Mn²⁺, Ca₆(PO₄)₃F:Mn²⁺, Ca₆(PO₄)₃F:Sb³⁺, Ca₆(PO₄)₃F:Sn²⁺, α-Ca₃(PO₄)₂:Eu²⁺, β-Ca₃(PO₄)₂:Eu²⁺, Ca₂P₂O₇:Eu²⁺, Ca₂P₂O₇:Eu²⁺, Mn²⁺, CaP₂O₆:Mn²⁺, α-Ca₃(PO₄)₂:Pb²⁺, α-Ca₃(PO₄)₂:Sn²⁺, β-Ca₃(PO₄)₂:Sn²⁺, β-Ca₂P₂O₇:Sn, Mn, α-Ca₃(PO₄)₂:Tr, CaS:Bi³⁺, CaS:Bi³⁺, Na, CaS:Ce³⁺, CaS:Eu²⁺, CaS:Cu⁺, Na⁺, CaS:La³⁺, CaS:Mn²⁺, CaSO₄:Bi, CaSO₄:Ce³⁺, CaSO₄:Ce³⁺, Mn²⁺, CaSO₄:Eu²⁺, CaSO₄:Eu²⁺, Mn²⁺, CaSO₄:Pb²⁺, CaS:Pb²⁺, CaS:Pb²⁺, Cl, CaS:Pb²⁺, Mn²⁺, CaS:Pr³⁺, Pb²⁺, Cl, CaS:Sb³⁺, CaS:Sb³⁺, Na, CaS:Sm³⁺, CaS:Sn²⁺, CaS:Sn²⁺, F, CaS:Tb³⁺, CaS:Tb³⁺, Cl, CaS:Y³⁺, CaS:Yb²⁺, CaS:Yb²⁺, Cl, CaSiO₃:Ce³⁺, Ca₃SiO₄Cl₂:Eu²⁺, Ca₃SiO₄Cl₂:Pb²⁺, CaSiO₃:Eu²⁺, CaSiO₃:Mn²⁺, Pb, CaSiO₃:Pb²⁺, CaSiO₃:Pb²⁺, Mn²⁺, CaSiO₃:Ti⁴⁺, CaSr₂(PO₄)₂:Bi³⁺, β-(Ca, Sr)₃(PO₄)₂:Sn²⁺Mn²⁺, CaTi_(0,9)Al_(0,1)O₃:Bi³⁺, CaTiO₃:Eu³⁺, CaTiO₃:Pr³⁺, Ca₅(VO₄)₃Cl, CaWO₄, CaWO₄:Pb²⁺, CaWO₄:W, Ca₃WO₆:U, CaYAlO₄:Eu³⁺, CaYBO₄:Bi³⁺, CaYBO₄:Eu³⁺, CaYB_(0,8)O_(3,7):Eu³⁺, CaY₂ZrO₆:Eu³⁺, (Ca, Zn, Mg)₃(PO₄)₂:Sn, CeF₃, (Ce, Mg)BaAl₁₁O₁₈:Ce, (Ce, Mg)SrAl₁₁O₁₈:Ce, CeMgAl₁₁O₁₉:Ce:Tb, Cd₂B₆O₁₁:Mn²⁺, CdS:Ag⁺, Cr, CdS:In, CdS:In, CdS:In, Te, CdS:Te, CdWO₄, CsF, CsI, CsI:Na⁺, CsI:TI, (ErCl₃)_(0,25)(BaCl₂)_(0,75), GaN:Zn, Gd₃Ga₆O₁₂:Cr³⁺, Gd₃Ga₅O₁₂:Cr, Ce, GdNbO₄:Bi³⁺, Gd₂O₂S:Eu³⁺, Gd₂O₂SPr³⁺, Gd₂O₂S:Pr, Ce, F, Gd₂O₂S:Tb³⁺, Gd₂SiO₆:Ce³⁺, KAI₁₁O₁₇:TI⁺, KGa₁₁O₁₇:Mn²⁺, K₂La₂Ti₃O₁₀:Eu, KMgF₃:Eu²⁺, KMgF₃:MnO²⁺, K₂SiF₆:Mn⁴⁺, LaAl₃B₄O₁₂:Eu³⁺, LaAlB₂O₆:Eu³⁺, LaAlO₃:Eu³⁺, LaAlO₃:Sm³⁺, LaAsO₄:Eu³⁺, LaBr₃:Ce³⁺, LaBO₃:Eu³⁺, (La, Ce, Tb)PO₄:Ce:Tb, LaCl₃:Ce³⁺, La₂O₃:Bi³⁺, LaOBr:Tb³⁺, LaOBr:Tm³⁺, LaOCl:Bi³⁺, LaOCl:Eu³⁺, LaOF:Eu³⁺, La₂O₃:Eu³⁺, La₂O₃:Pr³⁺, La₂O₂S:Tb³⁺, LaPO₄:Ce³⁺, LaPO₄:Eu³⁺, LaSiO₃Cl:Ce³⁺, LaSiO₃Cl:Ce³⁺, Tb³⁺, LaVO₄:Eu³⁺, La₂W₃O₁₂:Eu³⁺, LiAlF₄:Mn²⁺, LiAl₆O₈:Fe³⁺, LiAlO₂:Fe³⁺, LiAlO₂:Mn²⁺, LiAl₆O₈:Mn²⁺, Li₂CaP₂O₇:Ce³⁺, Mn²⁺, LiCeBa₄Si₄O₁₄:Mn²⁺, LiCeSrBa₃Si₄O₁₄:Mn²⁺, LiInO₂:Eu³⁺, LiInO₂:Sm³⁺, LiLaO₂:Eu³⁺, LuAlO₃:Ce³⁺, (Lu, Gd)₂SiO₅:Ce³⁺, Lu₂SiO₅:Ce³⁺, Lu₂Si₂O₇:Ce³⁺, LuTaO₄:Nb⁵⁺, Lu_(1-x)Y_(x)AlO₃:Ce³⁺, MgAl₂O₄:Mn²⁺, MgSrAl₁₀O₁₇:Ce, MgB₂O₄:Mn²⁺, MgBa₂(PO₄)₂:Sn²⁺, MgBa₂(PO₄)₂:U, MgBaP₂O₇:Eu²⁺, MgBaP₂O₇:Eu²⁺, Mn²⁺, MgBa₃Si₂O₈:Eu²⁺, MgBa(SO₄)₂:Eu²⁺, Mg₃Ca₃(PO₄)₄:Eu²⁺, MgCaP₂O₇:Mn²⁺, Mg₂Ca(SO₄)₃:Eu²⁺, Mg₂Ca(SO₄)₃:Eu²⁺, Mn², MgCeAl₁₁O₁₉:Tb³⁺, Mg₄(F)GeO₆:Mn²⁺, Mg₄(F)(Ge, Sn)O₆:Mn²⁺, MgF₂:Mn²⁺, MgGa₂O₄:Mn²⁺, Mg₈Ge₂O₁₁F₂:Mn⁴⁺, MgS:Eu²⁺, MgSiO₃:Mn²⁺, Mg₂SiO₄:Mn²⁺, Mg₃SiO₃F₄:Ti⁴⁺, MgSO₄:Eu₂₊, MgSO₄:Pb²⁺, (Mg, Sr)Ba₂Si₂O₇:Eu²⁺, MgSrP₂O₇:Eu²⁺, MgSr₆(PO₄)₄:Sn²⁺, MgSr₃Si₂O₈:Eu²⁺, Mn²⁺, Mg₂Sr(SO₄)₃:Eu²⁺, Mg₂TiO₄:Mn⁴⁺, MgWO₄, MgYBO₄:Eu³⁺, Na₃Ce(PO₄)₂:Tb³⁺, NaI:TI, Na_(1,23)K_(0,42)Eu_(0,12)TiSi₄O₁₁:Eu³⁺, Na_(1,23)K_(0,42)Eu_(0,12)TiSi₅O₁₃.xH₂O:Eu³⁺, Na_(1,29)K_(0,46)Er_(0,08)TiSi₄O₁₁:Eu³⁺, Na₂Mg₃Al₂Si₂O₁₀:Tb, Na(Mg_(2-x)Mn_(x))LiSi₄O₁₀F₂:Mn, NaYF₄:Er³⁺, Yb³⁺, NaYO₂:Eu³⁺, P46(70%)+P47 (30%), SrAl₁₂O₁₉:Ce³⁺, Mn²⁺, SrAl₂O₄:Eu²⁺, SrAl₄O₇:Eu³⁺, SrAl₁₂O₁₉:Eu²⁺, SrAl₂S₄:Eu²⁺, Sr₂B₅O₉Cl:Eu²⁺, SrB₄O₇:Eu²⁺ (F, Cl, Br), SrB₄O₇:Pb²⁺, SrB₄O₇:Pb²⁺, Mn²⁺, SrB₈O₁₃:Sm²⁺, Sr_(x)Ba_(y)Cl_(z)Al₂O_(4-z/2):Mn²⁺, Ce³⁺, SrBaSiO₄:Eu²⁺, Sr(Cl, Br, I)₂:Eu²⁺ in SiO₂, SrCl₂:Eu²⁺ in SiO₂, Sr₅Cl(PO₄)₃:Eu, Sr_(w)F_(x)B₄O_(6.5):Eu²⁺, Sr_(w)F_(x)B_(y)O_(z):Eu²⁺, Sm²⁺, SrF₂:Eu²⁺, SrGa₁₂O₁₉:Mn²⁺, SrGa₂S₄:Ce³⁺, SrGa₂S₄:Eu²⁺, SrGa₂S₄:Pb²⁺, SrIn₂O₄:Pr³⁺, Al³⁺, (Sr, Mg)₃(PO₄)₂:Sn, SrMgSi₂O₆:Eu²⁺, Sr₂MgSi₂O₇:Eu²⁺, Sr₃MgSi₂O₈:Eu²⁺, SrMoO₄:U, SrO.3B₂O₃:Eu²⁺,Cl, β-SrO.3B₂O₃:Pb²⁺, β-SiO.3B₂O₃:Pb²⁺, Mn²⁺, α-SrO.3B₂O₃:Sm²⁺, Sr₆P₅BO₂₀:Eu, Sr₅(PO₄)₃Cl:Eu²⁺, Sr₆(PO₄)₃Cl:Eu²⁺, Pr³⁺, Sr₆(PO₄)₃Cl:Mn²⁺, Sr₅(PO₄)₃Cl:Sb³⁺, Sr₂P₂O₇:Eu²⁺, β-Sr₃(PO₄)₂:Eu²⁺, Sr₆(PO₄)₃F:Mn²⁺, Sr₆(PO₄)₃F:Sb³⁺, Sr₅(PO₄)₃F:Sb³⁺, Mn²⁺, Sr₆(PO₄)₃F:Sn²⁺, Sr₂P₂O₇:Sn²⁺, β-Sr₃(PO₄)₂:Sn²⁺, β-Sr₃(PO₄)₂:Sn²⁺, Mn²⁺(Al), SrS:Ce³⁺, SrS:Eu²⁺, SrS:Mn²⁺, SrS:Cu⁺, Na, SrSO₄:Bi, SrSO₄:Ce³⁺, SrSO₄:Eu²⁺, SrSO₄:Eu²⁺, Mn²⁺, Sr₅Si₄O₁₀C₁₆:Eu²⁺, Sr₂SiO₄:Eu²⁺, SrTiO₃:Pr³⁺, SrTiO₃:Pr³⁺, Al³⁺, Sr₃WO₆:U, SrY₂O₃:Eu³⁺, ThO₂:Eu³⁺, ThO₂:Pr³⁺, ThO₂:Tb³⁺, YAl₃B₄O₁₂:Bi³⁺, YAl₃B₄O₁₂:Ce³⁺, YAl₃B₄O₁₂:Ce³⁺, Mn, YAl₃B₄O₁₂:Ce³⁺, Tb³⁺, YAl₃B₄O₁₂:Eu³⁺, YAl₃B₄O₁₂:Eu³⁺, Cr³⁺, YAl₃B₄O₁₂:Th⁴⁺, Ce³⁺, Mn²⁺, YAlO₃:Ce³⁺, Y₃Al₆O₁₂:Ce³⁺, Y₃Al₆O₁₂:Cr³⁺, YAlO₃:Eu³⁺, Y₃Al₅O₁₂:Eu³⁺, Y₄Al₂O₉:Eu³⁺, Y₃Al₆O₁₂:Mn⁴⁺, YAlO₃:Sm³⁺, YAlO₃:Tb³⁺, Y₃Al₅O₁₂:Tb³⁺, YAsO₄:Eu³⁺, YBO₃:Ce³⁺, YBO₃:Eu³⁺, YF₃:Er³⁺, Yb³⁺, YF₃:Mn²⁺, YF₃:Mn²⁺, Th⁴⁺, YF₃:Tm³⁺, Yb³⁺, (Y, Gd)BO₃:Eu, (Y, Gd)BO₃:Tb, (Y, Gd)₂O₃:Eu³⁺, Y_(1,34)Gd_(0,60)O₃(Eu, Pr), Y₂O₃:Bi³⁺, YOBrEu³⁺, Y₂O₃:Ce, Y₂O₃:Er³⁺, Y₂O₃:Eu³⁺(YOE), Y₂O₃:Ce³⁺, Tb³⁺, YOCl:Ce³⁺, YOCl:Eu³⁺, YOF:Eu³⁺, YOF:Tb³⁺, Y₂O₃:Ho³⁺, Y₂₂S:Eu³⁺, Y₂O₂S:Pr³⁺, Y₂O₂S:Tb³⁺, Y₂O₃:Tb³⁺, YPO₄:Ce³ ⁺, YPO₄:Ce³⁺,Tb³⁺, YPO₄:Eu³⁺, YPO₄:Mn²⁺, Th⁴⁺, YPO₄:V⁵⁺, Y(P, V)O₄:Eu, Y₂SiO₆:Ce³⁺, YTaO₄, YTaO₄:Nb⁵⁺, YVO₄:Dy³⁺, YVO₄:Eu³⁺, ZnAl₂O₄:Mn²⁺, ZnB₂O₄:Mn²⁺, ZnBa₂S₃:Mn²⁺, (Zn, Be)₂SiO₄:Mn²⁺, Zn₄Cd₆S:Ag, Zn_(0,6)C_(0,4)S:Ag, (Zn, Cd)S:Ag, Cl, (Zn, Cd)S:Cu, ZnF₂:Mn²⁺, ZnGa₂O₄, ZnGa₂O₄:Mn²⁺, ZnGa₂S₄:Mn²⁺, Zn₂GeO₄:Mn²⁺, (Zn, Mg)F₂:Mn²⁺, ZnMg₂(PO₄)₂:Mn²⁺, (Zn, Mg)₃(PO₄)₂:Mn²⁺, ZnO:Al³⁺, Ga³⁺, ZnO:Bi³⁺, ZnO:Ga³⁺, ZnO:Ga, ZnO—CdO:Ga, ZnO:S, ZnO:Se, ZnO:Zn, ZnS:Ag⁺, Cl⁻, ZnS:Ag, Cu, Cl, ZnS:Ag, Ni, ZnS:Au, In, ZnS—CdS (25-75), ZnS—CdS (50-50), ZnS—CdS (75-25), ZnS—CdS:Ag, Br, Ni, ZnS—CdS:Ag⁺,Cl, ZnS—CdS:Cu, Br, ZnS—CdS:Cu, I, ZnS:Cl⁻, ZnS:Eu²⁺, ZnS:Cu, ZnS:Cu⁺, Al³⁺, ZnS:Cu⁺, Cl⁻, ZnS:Cu, Sn, ZnS:Eu²⁺, ZnS:Mn²⁺, ZnS:Mn, Cu, ZnS:Mn²⁺, Te²⁺, ZnS:P, ZnS:P³⁻, Cl⁼, ZnS:Pb²⁺, ZnS:Pb²⁺, Cl⁻, ZnS:Pb, Cu, Zn₃(PO₄)₂:Mn²⁺, Zn₂SiO₄:Mn²⁺, Zn₂SiO₄:Mn²⁺, As⁵⁺, Zn₂SiO₄:Mn, Sb₂O₂, Zn₂SiO₄:Mn²⁺, P, Zn₂SiO₄:Ti⁴⁺, ZnS:Sn²⁺, ZnS:Sn, Ag, ZnS:Sn²⁺, Li⁺, ZnS:Te, Mn, ZnS—ZnTe:Mn²⁺, ZnSe:Cu⁺, Cl and/or ZnWO₄.

Finally, the present invention provides a method for producing an LED comprising the following steps:

-   -   (a) applying a formulation according to the invention to an LED         precursor; and     -   (b) curing the formulation at a temperature of 70 to 300° C. for         a period of 1 to 24 h.

Preferably, the LED precursor contains a semiconductor light source (LED chip) and/or lead frame and/or gold wire and/or solder (flip chip). The LED precursor may further optionally contain a converter and/or a primary optic and/or a secondary optic.

The converter layer may be arranged either directly on a semiconductor light source (LED chip) or alternatively remote therefrom, depending on the respective type of application. The encapsulation material forms a barrier against the external environment of the LED device, thereby protecting the converter and/or the LED chip. The encapsulating material is preferably in direct contact with the converter and/or the LED chip. The encapsulation material can be part of an LED device comprising an LED chip and/or lead frame and/or gold wire, and/or solder (flip chip), the filling material, converter and a primary and secondary optic.

It is preferred that the formulation which is applied in step (a) to an LED precursor forms part of a converter layer. It may be further preferred that the converter layer is in direct contact to an LED chip or is arranged remote therefrom.

Preferably, the converter layer further comprises a converter such as a phosphor and/or quantum material as defined above.

It is further preferred that the formulation is applied in step (a) as a layer in a thickness of 1 μm to 1 cm, more preferably of 10 μm to 1 mm to the LED.

In a preferred embodiment, the formulation is applied as a thin layer having a thickness of 1 μm to 200 μm, more preferably of 5 μm to 150 μm and most preferably of 10 μm to 100 μm. In an alternative preferred embodiment, the formulation is applied as a thick layer having a thickness of 200 μm to 1 cm, more preferably of 200 μm to 5 mm and most preferably of 200 μm to 1 mm.

The formulation of the invention may be applied by any suitable application method such as, for example, dispensing, screen printing, stencile printing, spray coating, slot coating and other methods. Alternatively, the formulation may be applied by any other suitable method, such as spin coating or ink-jet printing.

In case of dispensing a formulation with a high content of polymer and surface-modified nanoparticle is used. In case of screen printing a formulation with a certain higher viscosity is required. The viscosity can be adjusted by controlling the molecular weight of the polymer or by adding small amounts of solvents.

In case of spray coating a rather high dilution is needed, typically a spray coating formulation contains a total solvent content of 70-95 weight %. Since the solvent content in spray coating formulations is very high, spray coating formulations are very sensitive to the type of solvents. It is general knowledge that spray coating formulations are made of mixtures of high and low boiling solvents (e.g. Organic Coatings: Science and Technology, Z. W. Wicks et al., page 482, 3^(rd) Edition (2007), John Wiley & Sons, Inc.).

For example, it is preferred that the total content of the polymer, the surface-modified nanoparticles and the converter is in the range from 70 to 99.9 weight %, more preferably from 90 to 99.9 weight %, if dispensing is used. A typical solution for dispensing contains 10 to 35 weight % polymer, 25 to 40 weight % surface-modified nanoparticles, 30 to 50 weight % converter, <1 weight % solvent and <1 weight % other additives, with the respective weight percentages of the components of the dispensing formulation adding up to 100 weight %. The solvent is either a pure solvent or a mixture of several solvents as described above.

For example, it is preferred that the total content of the polymer, the surface-modified nanoparticles and the converter is in the range from 50 to 99.9 weight %, more preferably from 70 to 99.9 weight %, if screen printing or stencile printing is used. A typical solution for screen printing or stencile printing contains 10 to 15 weight % polymer, 20 to 30 weight % surface-modified nanoparticles, 40 to 60 weight % converter, 10 to 15 weight % solvent and <1 weight % other additives, with the respective weight percentages of the components of the screen printing or stencile printing formulation adding up to 100 weight %. The solvent is either a pure solvent or a mixture of several solvents as described above.

For example, it is preferred that the total content of the polymer, the surface-modified nanoparticles and the converter is in the range from 5 to 30 weight %, more preferably from 5 to 25 weight % and most preferably from 5 to 20 weight %, if spray coating is used. A typical solution for spray coating contains 2 to 5 weight % polymer, 4 to 12 weight % surface-modified nanoparticles, 6 to 20 weight % converter, 70 to 90 weight % solvent and <1 weight % other additives, with the respective weight percentages of the components of the spray coating formulation adding up to 100 weight %. The solvent is either a pure solvent or a mixture of several solvents as described above.

For example, it is preferred that the total content of the polymer, the surface-modified nanoparticles and the converter is in the range from 50 to 99.9 weight %, more preferably from 70 to 99 weight %, if slot coating is used. A typical solution for slot coating contains 10 to 15 weight % polymer, 20 to 30 weight % surface-modified nanoparticles, 40 to 60 weight % converter, 5 to 15 weight % solvent and <1 weight % other additives, with the respective weight percentages of the components of the slot coating formulation adding up to 100 weight %. The solvent is either a pure solvent or a mixture of several solvents as described above.

Suitable formulations preferably have a viscosity of at least 1 mPa·s and of at most 100,000 mPa·s, determined as described in the test methods. During the application of the formulation the viscosity of the formulation may optionally be modified by changing the temperature at which the composition is deposited, for example, between 10° C. and 60° C. A low viscosity is usually in the range from 1 to 100 mPa·s, whereas a high viscosity is usually more than 100 mPa·s.

A preferred solvent system for spray coating application is made up of two groups of solvent(s) A) and B). A) is one solvent or a mixture of two or more solvents characterized by a boiling point of <90° C. Preferred solvents of group A) are esters like methyl acetate or ethyl acetate, ethers like THF or ketones like methyl-ethyl ketone. B) is one solvent or a mixture of two or more solvents characterized by a boiling point of >90° C. Preferred solvents of group B) are esters like butyl acetate, ethers like di-butyl ether and alkanes like heptane, octane, nonane or decane, and aromatic solvents like benzene, toluene or xylene.

After having been applied to an LED precursor in step (a), the formulation is cured in step (b) at a temperature of 70 to 300° C. for a period of 1 h to 24 h.

Preferably, the curing in step (b) is carried out on a hot plate, in a furnace, or in a climate chamber.

Preferably, the curing in step (b) is carried out on a hot plate at a temperature of 100 to 280° C., more preferably from 120 to 270° C., and most preferably from 150 to 250° C.

In an alternative preferred embodiment, the curing in step (b) is carried out in a furnace at a temperature of 100 to 280° C., more preferably from 120 to 270° C., and most preferably from 150 to 250° C.

In an alternative preferred embodiment, the curing in step (b) is carried out in a climate chamber having a relative humidity in the range from 50 to 99%, more preferably from 60 to 95%, and most preferably from 80 to 90%, at a temperature from 70 to 95° C., more preferably from 80 to 90° C.

Preferably, the curing time is from 2 to 20 h, more preferably from 3 to 18 h, and most preferably from 4 to 16 h, depending on the application thickness, the monomer composition of the polymer and the curing method.

The LED according to the present invention may, for example, be used for backlights for liquid crystal (LC) displays, traffic lights, outdoor displays, billboards, general lighting, to name only a few non-limiting examples.

A typical LED package according to the invention comprises an LED chip, and/or a lead frame and/or gold wire and/or solder (flip chip) and/or the filling material, converter, the present encapsulation material and a primary and secondary optic. The encapsulation material has the function of a surface protection material against external environmental influences and guarantees long term reliability in particular aging stability. For example, in accordance with the present invention a light emitting diode is constructed similarly to the ones described in U.S. Pat. Nos. 6,274,924 B1 and 6,204,523 B1.

Moreover, a LED filament as described in US 2014/0369036 A1 may be prepared using the present encapsulation material as a package adhesive layer. Such LED filaments include a substrate, a light emitting unit secured onto at least one side surface of the substrate, and a package adhesive layer surrounded on the periphery of the light emitting unit. The substrate is configured to be of an elongated bar construction. The emitting unit includes a plurality of blue light chips and red light chips regularly distributed on the substrate and sequentially connected to one another in series. The package adhesive layer is made from the encapsulation material according to the present invention containing a converter.

The present invention is further illustrated by the examples following hereinafter which shall in no way be construed as limiting. The skilled person will acknowledge that various modifications, additions and alternations may be made to the invention without departing from the spirit and scope of the invention as defined in the appended claims.

Test Methods

Molecular weights of the polymers were determined by GPC against a polystyrene standard. As eluent a mixture of tetrahydrofuran and 1.45 weight % (relative to the total weight of the eluent) hexamethyldisilazane was used. Columns were Shodex KS-804 and 2×KS-802 and KS-801. The detector was an Agilent 1260 refractive index detector.

Viscosity was determined using a Brookfield Rheometer R/S plus with a Brookfield cone-type spindle RC3-50-1 at a rotation speed of 3 rpm and a temperature of 25° C.

EXAMPLES

The following siloxazane polymers consisting of up to four monomer units as shown in Table 2 were used in the examples:

—[Si(CH₃)₂—NH]_(a)—[Si(H)CH₃—NH]_(b)—[Si(CH₃)₂—O]_(c)—[SiH₂—NH]_(d)—

TABLE 2 Composition of Polymers 1 to 7. mol % mol % mol % mol % Molecular Polymer a b c d Weight [g/mol] Polymer 1⁽¹⁾ 50 50 0 0 5,500 Polymer 2⁽¹⁾ 25 25 50 0 7,700 Polymer 3⁽²⁾ 40 40 20 0 6,600 Polymer 4⁽¹⁾ 40 40 20 0 7,300 Polymer 5⁽¹⁾ 40 20 40 0 8,700 Polymer 6⁽²⁾ 20 40 40 0 10,100 Polymer 7⁽¹⁾ 30 20 30 20 8,300 ⁽¹⁾Random copolymer ⁽²⁾Block copolymer

Polymer 1 is available from MERCK Performance Materials Germany GmbH under the trade name Durazane 1050.

Preparation of Polymers 2, 4, 5 and 7 (Random Copolymers)

All starting materials were obtained from commercial sources, for example dichlorosilane from Gelest Inc. USA, dichloromethylsilane and dichloro-dimethylsilane from Sigma-Aldrich, and the a,w-dichloro-dimethylsilicones from ABCR.

General Procedure: A 4 I pressure vessel was charged with 1500 g of liquid ammonia at 0° C. and a pressure of between 3 bar and 5 bar. 850 g of a mixture of the dichlorosilane monomers as shown in Table 3 were slowly added over a period of 3 h. After stirring the resulting reaction mixture for an additional 3 h the stirrer was stopped and the lower phase isolated and evaporated to remove dissolved ammonia. After filtration a colourless viscous oil remained.

TABLE 3 Monomers used for preparation of Polymers 2, 4, 5 and 7. Polymer Monomers Polymer 2 250 g Cl₂Si(H)CH₃, 600 g Cl—[Si(CH₃)₂—O]—Si(CH₃)₂—Cl Polymer 4 347 g Cl₂Si(H)CH₃, 194 g Cl₂Si(CH₃)₂, 307 g Cl—Si(CH₃)₂—O—Si(CH₃)₂—Cl Polymer 5 88 g Cl₂Si(H)CH₃, 662 g Cl—Si(CH₃)₂—O—Si(CH₃)₂—Cl Polymer 7 163 g Cl₂SiH₂, 185 g Cl₂Si(H)CH₃, 498 g Cl—Si(CH₃)₂—O—Si(CH₃)₂—Cl

Preparation of Polymers 3 and 6 (Block Copolymers)

Starting materials were obtained from commercial sources, for example dichloromethylsilane and dichloro-dimethylsilane from Sigma-Aldrich, and the α,ω-bishydroxy-dimethylsilicones from ABCR.

General procedure: A 2 I flask was charged under nitrogen atmosphere with 1000 g n-heptane and a mixture of the dichlorosilane monomers and the silanol-terminated polydimethylsiloxane as shown in Table 4. At a temperature of 0° C., ammonia was slowly bubbled through the solution for 6 h. Precipitation of ammonium chloride was observed. The solid ammonium chloride was removed by filtration, yielding a clear filtrate, from which the solvent was removed by evaporation under reduced pressure. A colourless low viscous liquid was obtained.

TABLE 4 Monomers used for preparation of Polymers 3 and 6. Polymer Monomers Polymer 3 20.6 g Cl₂Si(H)CH₃, 24.9 g Cl₂Si(CH₃)₂, 5.8 g HO—[Si(CH₃)₂—O]₅—H Polymer 6 26.2 g Cl₂Si(H)CH₃, 15.4 g Cl₂Si(CH₃)₂, 16.8 g HO—[Si(CH₃)₂—O]₄₅—H

The molecular weight was analyzed using the following GPC conditions: the eluent was a mixture of THF and 1.45 weight % hexamethyldisilazane, the columns were Shodex KS-804 and 2×KS-802 and KS-801 and the detector was an Agilent 1260 Refractive Index Detector. The calibration was done with polystyrene standards.

Surface-modified nanoparticle dispersions in organic solvents were prepared using the following general procedure:

The following raw materials were used: a water based TiO₂ dispersion at 20 weight % available from Sigma-Aldrich, solid BaTiO₃ nanoparticles available from US Research Nanomaterials Inc. and solid AlN nanoparticles available from SkySpring Nanomaterials Inc.

In case the nanoparticles are available as a solid material, they were dispersed in a 1:3 water/isopropanole mixture at a concentration of 5 weight % by ultrasonic treatment. In case the nanoparticles are available as a water based dispersion, the solvent was partially changed to isopropanol by distillation so that a ratio of isopropanol:water >75:25 is obtained. In case the nanoparticles are available as an alcohol based dispersion, the material was used as delivered. The solid content of the nanoparticle dispersion was adjusted to 20 weight % either by dilution or by evaporating a part of the solvent. To 100 g of the 20 weight % nanoparticle dispersion 7 g of water was added and the temperature was increased to 60° C. At 60° C. a mixture of 1.5 g trimethyl-methoxysilane and 3.0 g n-hexyl-trimethoxysilane was added continuously over a period of 4 h. The mixture was additionally stirred for 4 h at 60° C. Then 150 g of PGMEA was added and the dispersion was concentrated by evaporation at 50° C. and a pressure of <40 mbar to 100 g. An additional amount of 150 g PGMEA was added and the dispersion was again concentrated by evaporation at 50° C. and a pressure of <40 mbar to 100 g. Finally, 100 g of a ca. 23% concentrated surface coated nanoparticle dispersion in PGMEA was obtained. The appearance of the dispersion is clear to opalescent, depending on the particle size.

Dispersion 1: TiO₂ nanoparticle dispersion at 20 weight % in PGMEA

Dispersion 2: BaTiO₃ nanoparticle dispersion at 20 weight % in PGMEA

Dispersion 3: AlN nanoparticle dispersion at 20 weight % in PGMEA

In the following, formulations for an encapsulation material were prepared by mixing a siloxazane polymer with a surface-modified nanoparticle dispersion. The refractive index of the encapsulation material was measured by spin coating the formulation on a 3 inch Si wafer at a film thickness of 1 μm and curing the film on a hotplate at 150° C. for 4 h. The measurement tool was a Prism Coupler Model 2010/M of the company

Metricon working at 594 nm at 25° C. Table 5 shows the respective weight ratios of the polymers and surface-modified nanoparticles.

TABLE 5 Formulations for encapsulation material and refractive index. Refractive Index at 25° C. and 594 Formulation nm A: Polymer 1 + Dispersion 1 at a weight ratio of 1:1.5 1.62 B: Polymer 1 + Dispersion 2 at a weight ratio of 1:1.5 1.61 C: Polymer 1 + Dispersion 3 at a weight ratio of 1:1.5 1.60

The refractive index of the encapsulation material can be adjusted by varying the ratio of the siloxazane polymer to the surface-modified nanoparticles. Polymer 1 and Polymer 2 were mixed with Dispersion 1 and Dispersion 2 in different ratios, respectively, as shown in Tables 6 and 7.

TABLE 6 Weight ratio of Polymer 1 and Dispersion 1. Weight Ratio Refractive Index Polymer 1:Dispersion 1 at 594 nm and 25° C. 100:0  1.50 50:50 1.57 30:70 1.67 20:80 1.72

TABLE 7 Weight ratio of Polymer 2 and Dispersion 2. Weight Ratio Refractive Index Polymer 2:Dispersion 2 at 594 nm at 25° C. 100:0  1.48 50:50 1.57 30:70 1.63 20:80 1.69

The refractive index of any material is to a certain extent always temperature dependent. For an LED application, a change in the refractive index of the encapsulant/binder changes the optical conditions. Thus, the colour and brightness of an LED device are temperature dependent. Therefore, encapsulants/binders having a low temperature dependence of the refractive index (which usually decreases with increasing temperature) are preferred. As shown in FIG. 4, the siloxazane based materials exhibit a significantly smaller decrease in refractive index (RI) when heated in comparison to methyl- and phenylsilicones.

To show its usefulness for LED devices, the polymer in PGMEA and the surface modified silicone capped nanoparticles in PGMEA were blended with phosphor light converter particles (isiphor® YYG 545 200, available from Merck KGaA) in weight ratios ranging from 1:2 to 1:4, diluted with ethyl acetate and the blend then spray coated as a 40 μm to 80 μm thick layer onto an LED chip mounted onto an LED package (available from Excelitas). For curing the polymer the LED was then placed on a hotplate at 150° C. for 8 hours.

The amount of phosphor on the LED chip was adjusted to reach a colour point of x=0.350 and y=0.330 according to the CIE definition. The LEDs were operated at a current of 1.5 A at ambient conditions for 1000 h and the change in colour coordinates was measured. A generally tolerated deviation of colour coordinates after 1000 h is +/−1%. As reference materials methylsilicone (OE-6370, DowCorning, refractive index=1.41) and phenylsilicone (OE-6550 DowCorning, refractive index=1.54) were used. The measured colour point deviation is shown in subsequent Table 8.

TABLE 8 Deviation of colour point. Δx/Δy Formulation (weight ratio) after 1,000 h⁽¹⁾ phenylsilicone:phosphor = 1:3 +0.008/+0.010 methylsilicone:phosphor = 1:3 +0.003/+0.002 phenylsilicone:Dispersion 1:phosphor = 1:1:3.5 _⁽²⁾ methylsilicone:Dispersion 1:phosphor = 1:1:3.5 _⁽²⁾ Polymer 4:phosphor = 1:3 +0.002/+0.003 Polymer 6:phosphor = 1:3 +0.003/+0.003 Polymer 4:Dispersion 1:phosphor = 1:1:3.5 +0.003/+0.002 Polymer 5:Dispersion 2:phosphor = 1:2:4 +0.003/+0.003 Polymer 6:Dispersion 3: phosphor = 1:2:4 +0.004/+0.004 ⁽¹⁾Measurement error = +/− 0.001 ⁽²⁾Methyl- or phenylsilicone is not miscible with surface-modified nanoparticles contained in Dispersion 1, 2 and 3. After mixing or after drying agglomeration occurs and a white precipitate is formed.

These examples demonstrate the stability of the encapsulation material under LED conditions. Methylsilicone is known to have excellent stability, but a low refractive index of only 1.41. Phenylsilicones have refractive indices in the range of 1.54, however, their stability is much worse. As a consequence, a significant shift in colour coordinates is observed. The siloxazane-surface modified nanoparticle encapsulation materials show a stability comparable to methylsilicone and are able to cover a bigger range of refractive index from 1.45 up to 1.70.

The curing properties of pure siloxazane formulations and silioxazane formulations with surface-modified silicone capped nanoparticles was compared by pouring the pure siloxazane formulation and the silioxazane-surface-modified nanoparticle formulation at different mixing ratios in plain glass bowls and evaporating all solvent under vacuum and exclusion of moisture to give a film thickness of the solvent free material of 0.5 mm. The glass bowls are then placed on a hot-plate at 150° C. under ambient conditions for 4 hours and the stickiness of the film was checked (Table 9).

TABLE 9 Curing and film properties Material Film after 4 h @ 150° C. Polymer 6 (pure siloxazane) sticky Polymer 6:Dispersion 1 = 1:1 (w/w) slightly sticky Polymer 6:Dispersion 1 = 1:2 (w/w) dry

Hence, the addition of surface-modified nanoparticles accelerates the curing of the siloxazane polymer leading to an efficient LED manufacturing process with a high throughput.

Furthermore, the barrier properties towards water vapor were analyzed by coating the formulation on a 0.2 μm pore size PTFE filter disc, curing the material for 4 h at 150° C. (methyl silicone) or for 16 h in a climate chamber at 85° C. and 85% relative humidity (pure siloxazane and siloxazane-surface-modified nanoparticle formulation). The measurement of the water vapor transmission rate (WVTR) was carried out with a MOCON Permatron-W 1/50 at a temperature of 38° C. and a relative humidity of 90%. The materials were coated on a 0.2 μm pore size PTFE filter disc as a carrier at a film thickness of 100-150 μm. The number of the methyl silicone was normalized to 100% (Table 10).

TABLE 10 Water vapor transmission rate WVTR Material [%, methyl silicone set to 100%] methyl silicone⁽¹⁾ 100 phenyl silicone⁽²⁾ 27 pure siloxazane⁽³⁾ 15 Polymer 3:Dispersion 1 = 1:1 12 (w/w) ⁽¹⁾methyl silicone = Dow Corning OE 6370 ⁽²⁾phenyl silicone = Dow Corning OE 6550 ⁽³⁾polymer 3

As shown in Table 10 above, the siloxazane-surface-modified nanoparticle formulation provides a better protection against water vapor when compared with a pure siloxazane or methyl silicone formulation. Hence, the formulations according to the present invention allow a better protection of the light converter particles and prevents a possible degradation of the converter material by moisture, which usually results in a colour change as a consequence of reduced conversion efficiency of the degraded phosphor. 

1.-16. (canceled)
 17. A formulation comprising: a polymer comprising a first repeating unit U¹ and a second repeating unit U², wherein the first repeating unit U¹ is represented by formula (I) and the second repeating unit U² is represented by formula (II): —[SiR¹R²—NR⁵—]—  (I) —[SiR³R⁴—[O—SiR³R⁴—]_(a)—NR⁵—]—  (II) wherein R¹, R², R³, R⁴ and R⁵ are at each occurrence independently from each other selected from the group consisting of hydrogen, organyl and organoheteryl groups, and a is an integer from 1 to 60; and surface-modified nanoparticles, wherein the surface-modified nanoparticles do not contain any zirconium dioxide.
 18. The formulation according to claim 17, wherein the surface-modified nanoparticles are surface-modified nanoparticles containing one or more inorganic nanoparticle materials selected from M²O, M³ ₂O₃, M^(4a)O₂, M²M^(4b)O₃, M²S, M²SO₃, M²SO₄, M² ₂SiO₄, M³N, M^(4b)C, M^(4b)SiO₄ and diamond, wherein M² is a divalent metal element, M³ is a trivalent metal element, M^(4a) is a tetravalent metal element excluding Zr and M^(4b) is a tetravalent metal element.
 19. The formulation according to claim 18, wherein M² is a divalent metal element selected from the list consisting of Mg, Ca, Sr, Ba, Cr, Mn, Fe, Co, Ni, Cu, Zn, Cd, Hg, Sn and Pb; M³ is a trivalent metal element selected from the list consisting of Sc, Y, Lu, Cr, Mn, Fe, B, Al and Ga; M^(4a) is a trivalent metal element excluding Zr selected from the list consisting of Ti, Hf, Si, Ge and Sn; and M^(4b) is a tetravalent metal element selected from the list consisting of Ti, Zr, Hf, Si, Ge and Sn.
 20. The formulation according to claim 17, wherein the surface of the nanoparticles are modified with surface modifying agents selected from alkyl-alkoxysilanes, alkenyl-alkoxysilanes or aryl-alkoxysilanes.
 21. The formulation according to claim 17, wherein the polymer comprises at least one further repeating unit U¹ which is represented by formula (I), wherein the at least one further repeating unit U¹ is different from the first repeating unit U¹.
 22. The formulation according to claim 17, wherein R¹ and R² are at each occurrence independently from each other hydrogen or alkyl having 1 to 20 carbon atoms or phenyl.
 23. The formulation according to claim 17, wherein R³ and R⁴ are independently from each other hydrogen or alkyl having 1 to 40 carbon atoms or phenyl.
 24. The formulation according to claim 17, wherein R⁵ is at each occurrence independently hydrogen or alkyl having 1 to 20 carbon atoms or phenyl.
 25. The formulation according to claim 17, wherein said formulation comprises one or more solvent(s) selected from the group consisting of ethers, cyclic ethers, ketones, esters, mixed ether/ester solvents, hydrocarbons, aromatic solvents, wherein one or more hydrogen atoms in the solvent(s) may be optionally substituted by chlorine or fluorine atoms.
 26. A method for preparing the formulation according to claim 17, wherein a polymer containing a first repeating unit U¹ and a second repeating unit U² is mixed with a dispersion of surface-modified nanoparticles, wherein the surface-modified nanoparticles do not contain any zirconium dioxide.
 27. An encapsulation material for an LED, obtainable by (a) providing the formulation according to claim 17; and (b) curing said formulation at a temperature of 70 to 300° C. for a period of 1 to 24 h.
 28. A LED comprising the encapsulation material according to claim
 27. 29. The LED according to claim 28, wherein the encapsulation material is comprised in a converter layer.
 30. The LED according to claim 28, wherein the encapsulation material is comprised in a converter layer which comprises one or more converters selected from phosphors and/or quantum materials.
 31. A method for producing an LED comprising the steps of (a) applying a formulation according to claim 17 to an LED precursor; and (b) curing the formulation at a temperature of 70 to 300° C. for a period of 1 to 24 h.
 32. The method for producing an LED according to claim 31, wherein the formulation which is applied in step (a) to an LED precursor forms part of a converter layer which preferably comprises one or more converters selected from phosphors and/or quantum materials.
 33. The method for producing an LED according to claim 31, wherein the formulation is applied in step (a) by dispensing, screen printing, stencile printing, spray coating, slot coating, spin coating or ink-jet printing. 